CN104446325A - High temperature, contamination and slagging resistant ceramic paint as well as preparation method and application of high temperature, contamination and slagging resistant ceramic paint - Google Patents
High temperature, contamination and slagging resistant ceramic paint as well as preparation method and application of high temperature, contamination and slagging resistant ceramic paint Download PDFInfo
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- CN104446325A CN104446325A CN201410687121.8A CN201410687121A CN104446325A CN 104446325 A CN104446325 A CN 104446325A CN 201410687121 A CN201410687121 A CN 201410687121A CN 104446325 A CN104446325 A CN 104446325A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/32—Carbides; Nitrides; Borides ; Silicides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions 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 cold phosphate binders
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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Abstract
The invention provides high temperature, contamination and slagging resistant ceramic paint, as well as a preparation method and an application of the high temperature, contamination and slagging resistant ceramic paint and belongs to the technical field of special paint. The ceramic paint comprises the following ingredients by mass percentage: 15-30% of filling, 40-65% of adhesive agent and the balance of water, wherein the filling comprises 3-5% of zirconia, 3-5% of silicon carbide, 3-5% of silicon nitride, 1-3% of titanium dioxide, 2-4% of kaoline and 3-8% of rare earth oxide. The preparation method of the paint comprises the steps of mixing the adhesive agent with the water to prepare adhesive agent liquid, adding the filling refined into a particle size to be up to 50-900nm into the adhesive agent liquid, adding an assistant, uniformly mixing, filtering and packaging. The paint can be applied on the external surfaces of a boiler tube and a heater tube to form a ceramic coating to prepare the high-performance boiler tube and the heater tube.
Description
Technical field
The invention belongs to special coating technical field, be specifically related to a kind of high temperature resistant anti-Slagging ceramic coating and its preparation method and application.
Background technology
In the production run of station boiler, petroleum and petrochemical industry process furnace and commercial industry boiler etc., pulverized coal firing boiler (comprising fuel vapor heating furnace tube) stains and causes very big hidden danger to the safe operation of boiler, affect boiler and heater efficiency simultaneously, under high-temperature flue gas effect, be bonded on water wall or high temperature superheater and the lime-ash of heating furnace tube with tube wall, complicated chemical reaction can occur, form high temperature corrosion.Contamination, slagging scorification are generally considered to be the prelude of high temperature corrosion, Reasons of High Temperature Corrosion comprises sulphate corrosion, sulfide corrosion, chloride corrosion and reducing atmosphere corrosion etc., and wherein high-temperature sulfuric acid brine corrosion comprises again pyrosulphate burn into sulphate corrosion etc.High temperature heat exchange surface Slagging directly causes boiler and process furnace exchange capability of heat to decline, stove effect and reduction of exerting oneself, and then the heat exchange surface irregular boiler tube thermal stresses that causes of being heated is uneven and be heated irregular by heating working medium, simultaneously fire box temperature raise cause boiler tube overheating operation, NO_x formation and discharge aggravation and funnel temperature too high, the corrosion of Slagging aggravation heat exchange surface, these problems directly affect the safety in production of enterprise, energy-saving and emission-reduction, quality product and production capacity, reduce service life of equipment, bring heavy losses to enterprise.
For Slagging, traditional solution be strengthen blowing ash, adjust fuel, the decoking agent that puts into operation, machinery beats Jiao etc., this brings the financial loss of persistence to enterprise, and potential safety hazard still exists.
Ceramic coating is as a kind of new function material, the effect of high-temperature corrosion resistance and raising emittance can be played, but the ceramic coating of prior art cannot solve high contamination and high temperature corrosion particularly reductibility etching problem, therefore comprehensively above-mentioned functions can not be realized, and in use procedure, have that coating chaps, comes off, the situation of efflorescence in various degree, have a strong impact on the work-ing life of coating, these problems still cannot effectively solve at present.
Summary of the invention
For above shortcomings in prior art, the invention provides a kind of high temperature resistant anti-Slagging ceramic coating.
Another object of the present invention is to provide the preparation method of above-mentioned high temperature resistant anti-Slagging ceramic coating.
Another object of the present invention is to provide the application of above-mentioned high temperature resistant anti-Slagging ceramic coating.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of high temperature resistant anti-Slagging ceramic coating, comprises the following component by mass percentage: filler 15 ~ 30%, the water of binding agent 40 ~ 65% and surplus; Wherein filler comprises zirconium white 3 ~ 5%, silicon carbide 3 ~ 5%, silicon nitride 3 ~ 5%, titanium dioxide 1 ~ 3%, kaolin 2 ~ 4% and rare earth oxide 3 ~ 8%.
Inorganic coating at high temperature has the characteristics such as thermal conductive resin, wear-resistant, acid-alkali-corrosive-resisting.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, described binding agent is aluminium dihydrogen phosphate and silicon sol, and these two kinds of composition self fusing points are higher, and under high temperature, bonded energy is higher, not easily melts, and improves the thermotolerance of binding agent.Adopt mineral binder bond not only high temperature resistant, and at high temperature drying is rear and bond matrix power is strong, also can improve intensity and smooth finish, to strengthen stain resistance.The successful that these two kinds of binding agents share generation is better than adopting single binding agent, and at high temperature have good adhesive property, coating expansion rate is little, and between matrix, binding ability is strong.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, the mass percentage of described aluminium dihydrogen phosphate is 35 ~ 45%, and the mass percentage of silicon sol is 5 ~ 20%.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, described rare earth oxide is yttrium oxide, cerium oxide and europium sesquioxide.Can physical strength be improved by adding rare earth oxide, forming rare earth aluminate inhibiting grain growth when particularly sharing sinter with kaolin and aluminium dihydrogen phosphate, improving compactness, and then gain in strength and stain resistance.And three kinds of rare earth oxides are when sharing, its mutual promoting action, improves product performance further.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, the mass percentage of described yttrium oxide is 1 ~ 3%, and the mass percentage of cerium oxide is 1 ~ 3%, and the mass percentage of europium sesquioxide is 1 ~ 2%.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, also comprise more than one the auxiliary agent in dispersion agent, wetting agent and defoamer, auxiliary agent mass percentage is no more than 3%.The local defect that when auxiliary agent is mainly used to improve dispersiveness, wettability and avoid film, generation bubble causes.Dispersion agent, defoamer and wetting agent all can select this area conventional commercial commodity, and such as dispersion agent can select CF-10, Hensic H-4200 etc., and defoamer can select DF104, Hensic H-210, Hensic H-231 etc.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, the dispersion agent 0.5 ~ 1% by mass percentage is comprised, wetting agent 0.5 ~ 0.8% and defoamer 0.3 ~ 0.5%.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, copper-chrome black that mass percentage is no more than 5% is also comprised to improve high temperature resistant and corrosion resistance, to be no more than the boron nitride of 3% to improve hardness and to reduce surface free energy minimizing pickup in described filler, can be combined with rare-earth phase simultaneously and reduce sintering temperature, improve toughness of material to improve freedom from cracking and powder performance, with be no more than the wilkinite of 3% to improve sticking power, can containing the mixture of one or more in above-mentioned materials.
Preferably, in above-mentioned high temperature resistant anti-Slagging ceramic coating, the following component by mass percentage is comprised: filler 23.5 ~ 28.5%, the water of binding agent 53 ~ 59% and surplus; Wherein filler comprises zirconium white 3.5 ~ 4%, silicon carbide 2 ~ 2.5%, silicon nitride 3 ~ 4%, titanium dioxide 2 ~ 2.5%, kaolin 3 ~ 4% and rare earth oxide 4 ~ 5.5%, copper-chrome black 3 ~ 4%, boron nitride 1 ~ 2%, wilkinite 2 ~ 2.5%.
The preparation method of above-mentioned high temperature resistant anti-Slagging ceramic coating provided by the invention, binding agent is added water be mixed to get binding agent liquid, then filler thinning processing to granularity being reached 50 ~ 900nm joins in binding agent liquid, then adds auxiliary agent and stir, and filters encapsulation.
The present invention also provides above-mentioned high temperature resistant anti-Slagging ceramic coating preparing the application in generator tube and/or heating furnace tube, and ceramic coating is coated on generator tube and/or heating-furnace tube outer surface forms ceramic coating.
Compared with prior art, the present invention has following beneficial effect:
High temperature resistant anti-Slagging ceramic coating of the present invention can resistance to 1050 DEG C of high temperature, and still keep the high emissivity of more than 0.94 under high temperature, enhanced heat exchange; Surface energy is low, anti-Slagging; Coating integrates unreactiveness and passivation protection, has automatic cleaning action, effectively prevents Slagging, and the matrix of protection matrix, particularly metal material, improves the heat exchange efficiency of boiler, make heating surface more even; High-temperature corrosion resistance, long service life, uses easy, and practical application effect is obvious, is widely used in petroleum and petrochemical industry process furnace and station boiler boiler tube etc.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, to help understanding content of the present invention.
Binding agent is added water and is mixed to get binding agent liquid, then filler thinning processing to granularity being reached 50 ~ 900nm joins in binding agent liquid, then adds auxiliary agent as required and stir, and filters encapsulation, obtain ceramic coating of the present invention, each raw material of coating and consumption as shown in table 1 below.
Ceramic coating prepared by table 1 different components
By the coating in embodiment 1-7, coat HP-40WM tube skin, coating thickness is 30 ~ 50 microns, and surfacing post-drying solidification to be coated, carries out appearance detection.Coating after oven dry is placed in High Temperature Furnaces Heating Apparatus and is warming up to 1050 DEG C, insulation 3h, high temperature resistant test result display dope layer without coming off, ftracture, powder phenomenon-tion.Carry out the detection of emittance and thermal conductivity in addition, concrete outcome is in table 2.
Table 2 coating property detected result
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| 1050 DEG C of high temperature tests | Without cracking, without bubbling | Without cracking, without bubbling | Without cracking, without bubbling | Without cracking, without bubbling | Without cracking, without bubbling | There is cracking, micro-foaming | Crackly to split, micro-foaming |
| Emittance | 0.92 | 0.94 | 0.92 | 0.93 | 0.94 | 0.90 | 0.91 |
| Thermal conductivity (W/m/K) | 9 | 13 | 9 | 12 | 13 | 6 | 7 |
The coating of embodiment 1-7 carries out the detection of following items:
1, coating heterogeneous microstructure: coated substrates is HP-40WM boiler tube, and coat-thickness is about 100 μm, after using cutting machine and automatic metallic phase draft machine to process sample, observes coatingsurface and coating cross sections by scanning electronic microscope.Result shows the equal surfacing of embodiment 1-5 coating, does not find obvious crackle, and coating joint portion does not find that obvious crackle exists, and coating is combined with matrix well, and the tiny crack that embodiment 6 and 7 coatingsurface occurs is non-penetrating crack.The microtexture form of coating has material impact to coating use properties, and from microscopic appearance, several coating of embodiment 1-5 and matrix all have good combination, and this is conducive to the protection to matrix.
2, coating heat resistanceheat resistant alternation ability detects: test by GB4653 infrared radiation coating general technical specifications, sample is put into process furnace, and take out after 650 DEG C of insulation 30min, air blast cooling is to room temperature, be circulated to the defects such as peeling off appears in coating, crackle, and record number of times.According to test-results, embodiment 1-5 all meets standard-required, and wherein embodiment 2 and 4 effect is best, and embodiment 5 is respond well, and embodiment 6 and 7 does not meet standard-required.
Because coating of the present invention is mainly used on tubing, in order to verify the impact of corrosion product on coating, the following test of design: matrix selects 20G and high Cr steel, sample is put into process furnace, take out after 650 DEG C of insulation 30min, air blast cooling, to room temperature, is circulated to the defects such as peeling off appears in coating, crackle, and records number of times.Test-results shows, several coating heat resistanceheat resistant alternation ability is good, wherein 2,4 shows fabulous heat resistanceheat resistant alternation performance.
Table 3
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Number of times | 21 | 43 | 25 | 42 | 38 |
3, anti-coking slagging scorification test
Embodiment 1-5 coating sample and contrast pipe are run in testing table, contrast coating is managed with contrast.The more untreated tube surface dust stratification of pipe fitting after surface treatment is relatively thin; illustrate that resistive connection slag coating has the ability reducing Slagging; there is the heating surface ceramic coating of coating still bright; heating surface surface does not have oxidation corrosion phenomenon; and without coating heating surface coking and slagging and oxidation corruption phenomenon serious; illustrate that resistive connection slag coating protects heating surface in addition, the effect of resistance to high temperature corrosion.
4, resistance to high temperature corrosion test
Due to high-temperature corrosion in boiler complicated condition, testing laboratory lacks effective environmental simulation means, and the corrosion with salt coating method that this test and Selection is commonly used detects the high temperature resistance sulfur corrosion characteristic of embodiment 1-5 paint coatings.Temperature-rising method test is smeared, selected 650 DEG C of high-temperature sulfur corrosion test temperature, air atmosphere with saturated solution vitriol; Measure specimen surface and amass A, dip sodium sulfate and the potassium sulfate saturated aqueous solution of mol ratio 7:3 with writing brush, be evenly coated onto HP-40WM boiler tube specimen surface, the even salt film of one deck after oven dry, can be left.Subsequently sample is weighed, and be placed in 650 DEG C of air atmosphere, carry out corrosion test.Sample takes out after the scheduled time in insulation, again weighs after cooling, and then is coated with salt, dries, weighs, corrodes ...The data of surrosion process by formula (1).Etching time setting 80h, is once coated with salt at regular intervals and weighs, finally draw out corrosion kinetics curve according to data point.
△W
i=[(W
i+2-W
i)/A]- [(W
i+1-W
i)/A]×0.6 (1)
W in formula
ibe that before i-th corrosion, test specimen is weighed;
W
i+1be weighing after being coated with salt i-th time;
W
i+2be weighing after i-th corrosion;
A is total surface-area of test specimen;
0.6 for deducting the coefficient of salt membrane crystallization water.
Test-results shows that the coating of embodiment 1-5 all has good resistance to high temperature corrosion ability, and wherein the resistance to high temperature corrosion ability of embodiment 2 and 4 is best.
The practical application of high temperature resistant anti-Slagging ceramic coating:
Comparatively laboratory test is more complicated for boiler operation situation under actual condition, therefore chooses certain power plant 220 tons of/hour high pressure pulverized coal firing boilers and tests.This boiler uses bituminous coal mixed coal, and furnace wall cooling Slagging is serious, boiler maximum load 180 tons/hour, superheater over temperature, desuperheating water excess one times, funnel temperature 180 DEG C, has a strong impact on efficiency and exerts oneself.
Boiler tube substrate surface is after clean, and the coating segmentation of embodiment of the present invention 1-5 is sprayed at substrate surface, and coat-thickness is 30 ~ 50 microns, can heat up after surface drying with stove, the hot operation of equipment investment.
Use high temperature resistant anti-Slagging ceramic coating of the present invention blowing out inspection after a year, tube skin floats the thin and erasable of ash bed and flips and remove, and exposes ceramic coating, does not find that coatingsurface has cracking obscission; The most high force of boiler reaches at full capacity, and spray water flux returns to scope of design, and funnel temperature is down to 145 DEG C, and fuel saving and raising are exerted oneself successful, improve safety and economic benefit and the coal adaptability of unit operation.
Above-described embodiment is only for example of the present invention is clearly described, not limitation of the invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All within the spirit and principles in the present invention any apparent change of extending out or variation be still among the protection domain of the claims in the present invention.
Claims (10)
1. a high temperature resistant anti-Slagging ceramic coating, is characterized in that, comprises the following component by mass percentage: filler 15 ~ 30%, the water of binding agent 40 ~ 65% and surplus; Wherein filler comprises zirconium white 3 ~ 5%, silicon carbide 3 ~ 5%, silicon nitride 3 ~ 5%, titanium dioxide 1 ~ 3%, kaolin 2 ~ 4% and rare earth oxide 3 ~ 8%.
2. high temperature resistant anti-Slagging ceramic coating according to claim 1, it is characterized in that, described binding agent is aluminium dihydrogen phosphate and silicon sol.
3. high temperature resistant anti-Slagging ceramic coating according to claim 2, is characterized in that, the mass percentage of described aluminium dihydrogen phosphate is 35 ~ 45%, and the mass percentage of silicon sol is 5 ~ 20%.
4. high temperature resistant anti-Slagging ceramic coating according to claim 1, it is characterized in that, described rare earth oxide is yttrium oxide, cerium oxide and europium sesquioxide.
5. high temperature resistant anti-Slagging ceramic coating according to claim 4, is characterized in that, the mass percentage of described yttrium oxide is 1 ~ 3%, and the mass percentage of cerium oxide is 1 ~ 3%, and the mass percentage of europium sesquioxide is 1 ~ 2%.
6. high temperature resistant anti-Slagging ceramic coating according to claim 1, it is characterized in that, also comprise more than one the auxiliary agent in dispersion agent, wetting agent and defoamer, auxiliary agent mass percentage is no more than 3%.
7. high temperature resistant anti-Slagging ceramic coating according to claim 1, is characterized in that, also comprise in described filler mass percentage be no more than the copper-chrome black of 5%, the boron nitride being no more than 3% and be no more than in the wilkinite of 3% one or more.
8. high temperature resistant anti-Slagging ceramic coating according to claim 1, is characterized in that, comprise the following component by mass percentage: filler 23.5 ~ 28.5%, the water of binding agent 53 ~ 59% and surplus; Wherein filler comprises zirconium white 3.5 ~ 4%, silicon carbide 2 ~ 2.5%, silicon nitride 3 ~ 4%, titanium dioxide 2 ~ 2.5%, kaolin 3 ~ 4% and rare earth oxide 4 ~ 5.5%, copper-chrome black 3 ~ 4%, boron nitride 1 ~ 2%, wilkinite 2 ~ 2.5%.
9. the preparation method of the arbitrary described high temperature resistant anti-Slagging ceramic coating of claim 1 ~ 7, it is characterized in that, binding agent is added water and is mixed to get binding agent liquid, then filler thinning processing to granularity being reached 50 ~ 900nm joins in binding agent liquid, add auxiliary agent again to stir, filter encapsulation.
10. the arbitrary described high temperature resistant anti-Slagging ceramic coating of claim 1 ~ 7 is preparing the application in generator tube and/or heating furnace tube, and ceramic coating is coated on generator tube and/or heating-furnace tube outer surface forms ceramic coating.
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| CN201410687121.8A CN104446325B (en) | 2014-11-26 | 2014-11-26 | A kind of high temperature resistant anti-Slagging ceramic coating and its preparation method and application |
| PCT/CN2015/090214 WO2016082610A1 (en) | 2014-11-26 | 2015-09-22 | High temperature-, stain- and slagging-resistant ceramic coating and preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104446325B (en) * | 2014-11-26 | 2015-08-26 | 清大赛思迪新材料科技（北京）有限公司 | A kind of high temperature resistant anti-Slagging ceramic coating and its preparation method and application |
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| CN1046517A (en) * | 1990-03-24 | 1990-10-31 | 广州师范学院 | Refractory, energy saving and corrosion-resisting ceramics coating |
| CN103043995A (en) * | 2012-12-19 | 2013-04-17 | 青岛博益特生物材料有限公司 | Ceramic coating |
| CN103820021A (en) * | 2013-12-23 | 2014-05-28 | 杭州吉华高分子材料有限公司 | Non-stick ceramic paint and preparation method thereof |
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