CN115724659B - Multifunctional protective and energy-saving synergistic coating and preparation method thereof - Google Patents
Multifunctional protective and energy-saving synergistic coating and preparation method thereof Download PDFInfo
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- CN115724659B CN115724659B CN202211539139.4A CN202211539139A CN115724659B CN 115724659 B CN115724659 B CN 115724659B CN 202211539139 A CN202211539139 A CN 202211539139A CN 115724659 B CN115724659 B CN 115724659B
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- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 239000011248 coating agent Substances 0.000 title claims abstract description 110
- 230000001681 protective effect Effects 0.000 title claims abstract description 40
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- 239000011029 spinel Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 19
- 239000010431 corundum Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 17
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 17
- 239000000440 bentonite Substances 0.000 claims abstract description 16
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 16
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 8
- YQOPHINZLPWDTA-UHFFFAOYSA-H [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YQOPHINZLPWDTA-UHFFFAOYSA-H 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 6
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 230000003749 cleanliness Effects 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 238000005488 sandblasting Methods 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 3
- 241000209140 Triticum Species 0.000 claims 1
- 235000021307 Triticum Nutrition 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 239000002893 slag Substances 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000005855 radiation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000001595 mastoid Anatomy 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004092 self-diagnosis Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- -1 tetraethoxysilane compound Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a multifunctional protective and energy-saving synergistic coating which comprises the following raw materials in percentage by weight: 10-30% of spinel high-entropy ceramic, 2-4% of rare earth oxide, 10-12% of silicon oxide, 8-12% of aluminum oxide, 8-10% of aluminum nitride, 6-8% of cordierite, 3-4% of brown corundum, 0.5-2% of bentonite, 30-40% of composite binder, 0.4-0.6% of dispersing agent and 0.4-0.6% of defoaming agent. The invention also discloses a preparation method of the coating. The invention has the characteristics of coking slag prevention and high-temperature corrosion resistance.
Description
Technical Field
The invention relates to the technical field of high-temperature protective coatings of boiler radiation heating surfaces, in particular to a multifunctional protective and energy-saving synergistic coating and a preparation method thereof.
Background
Under the background of double carbon and increasingly strict environmental protection requirements, in order to realize ultra-low emission, most of domestic coal-fired power plants adopt a low-nitrogen combustion technology. However, the low-nitrogen combustion technology causes serious coking, slagging and high-temperature corrosion problems of heating surfaces (water wall pipes, high-temperature superheaters, high-temperature reheaters and burner nozzles), and the safety and the economical efficiency of the boiler are reduced due to coking and slagging and high-temperature corrosion of the heating surfaces of the coal-fired boiler.
Coking and slagging and high-temperature corrosion of a heating surface of a boiler are complex physical and chemical processes, and are closely related to factors such as the characteristics of combustion coal quality of the boiler, design parameters of the boiler, load conditions, flue gas temperature in the boiler, flue gas atmosphere, heating surface substrate temperature, operation combustion adjustment and the like. In order to avoid risks caused by coking, slag bonding and high-temperature corrosion and ensure safe operation of the boiler, a series of protection measures are adopted by the power plant. Spraying a protective coating on the surface of the heated surface is an important means for solving the problems.
Conventional nickel-based alloy coatings such as British ET-4 and the like are usually used at 1100 ℃ and can cause the coating to fall off when exceeding 1100 ℃, so that the application of the coating on industrial boilers is restricted. The binders commonly used for inorganic high temperature, corrosion and coking resistant coatings are silicates, silica sols, ethyl silicate and phosphates. The long-term use temperature of the four binders is 400-600 ℃, and the binders are commonly used in water-cooled wall areas with lower boiler temperature, and the coating performance is reduced or failed when the use temperature is exceeded. However, the central temperature of pulverized coal boilers is generally between 1400 ℃ and 1700 ℃, the ambient temperature of near wall areas is 1200 ℃, and even the wall temperature of high-temperature reheaters and high-temperature superheaters of some boilers exceeds 700 ℃. Therefore, in order to meet the protection requirement of the heating surface of the boiler, a multifunctional protection coating which has higher use temperature, coking slag resistance and high-temperature corrosion resistance needs to be developed.
The traditional solution is to thermally spray the metal matrix, and protect the metal matrix by using supersonic flame spraying, plasma spraying, laser cladding technology and the like. The invention patent CN104264102B discloses a preparation method of a nickel-based alloy coating on a boiler water wall, wherein a layer of composite coating is arranged on the surface of a tube panel of the boiler water wall, and the composite coating adopts supersonic electric arc spraying equipment to spray a layer of bonding bottom layer, and then spray a nickel-based alloy coating with high temperature corrosion resistance and wear resistance to form a double-layer structure. The invention patent CN114000088A discloses a coating for site protection of a water wall pipe of a power station boiler, which is obtained by sequentially carrying out supersonic arc spraying and secondary instant online remelting treatment on an iron-based amorphous composite powder core wire, and firstly proposes a method for site protection of a water wall system of the power station boiler by utilizing a remelted iron-based coating local reinforcement protection technology, so that the abrasion and corrosion problems in the operation process of the water wall of the boiler are effectively reduced. The invention patent CN107299255A discloses a nickel-based wire for corrosion prevention and spraying of a water-cooled wall of a biomass boiler, which comprises metallic chromium, metallic nickel, metallic titanium and rare earth elements, and the coating has good high-temperature oxidation resistance and hot corrosion resistance and can greatly prolong the service life of boiler equipment. The invention patent CN114164391A provides a high-temperature anti-coking electric arc spraying powder core wire for an electric pulverized coal boiler, and the prepared coating has excellent bonding strength and high-temperature anti-coking performance, is special for the electric pulverized coal boiler, replaces other anti-coking coatings on the market, and can greatly improve the anti-coking capability of a furnace tube of the pulverized coal boiler. However, the above-mentioned several coatings have single functions, narrow application surface, large environmental pollution, high cost, complex construction process, poor corrosion resistance effect and are not suitable for large-scale application.
Therefore, it is necessary to develop an environment-friendly coating technology which is multifunctional, environment-friendly, pollution-free, low in cost, simple in construction process, has coking residue prevention and high-temperature corrosion resistance, and can be suitable for various heating surfaces.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multifunctional protection and energy-saving synergistic coating with coking slag resistance and high-temperature corrosion resistance.
The invention aims to provide a preparation method of the multifunctional protective and energy-saving synergistic coating.
In order to solve the problems, the multifunctional protective and energy-saving synergistic coating provided by the invention is characterized in that: the coating consists of the following raw materials in percentage by weight: 10-30% of spinel high-entropy ceramic, 2-4% of rare earth oxide, 10-12% of silicon oxide, 8-12% of aluminum oxide, 8-10% of aluminum nitride, 6-8% of cordierite, 3-4% of brown corundum, 0.5-2% of bentonite, 30-40% of composite binder, 0.4-0.6% of dispersing agent and 0.4-0.6% of defoaming agent.
The spinel high-entropy ceramic is prepared from CuO, mnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 Any six of ZnO and MgO powder are used as raw materials, ball milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in an air atmosphere, and then cooling and grinding are carried out, so that the high-entropy oxide with the spinel structure and the particle size of 300-800 nm is obtained.
The rare earth oxide is any 1-2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and the particle size is 0.5-1.0 mu m.
The particle sizes of the silicon oxide and the aluminum oxide are 1 mu m; the grain size of the aluminum nitride is 200-300 nm; the particle sizes of the cordierite and the bentonite are 10 mu m; the grain size of the brown corundum is 1-2 mu m.
The composite binder is prepared from chromium aluminum phosphate and ethyl orthosilicate according to a weight ratio of 3:1 mass ratio, and stirring and mixing uniformly.
The dispersing agent is one of the following components of the Michael chemical HY-330A+HY-330B, di-high Dispers-760W and Kaimei KMT-3021.
The defoamer is one of Kelmeter KMT-2017, digaorex-902W and DigaTego 825.
The thickness of the coating is 100-200 mu m.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing according to a proportion;
preparing a coating:
firstly, dispersing agents and defoaming agents are sequentially added into a composite adhesive and fully stirred; then, adding the spinel Dan Gaoshang ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite in sequence, and dispersing uniformly at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and ball milling at 300-500 rpm for 3-5 hours to obtain a uniform multifunctional protective and energy-saving coating;
thirdly, adopting quartz stone or brown corundum with the particle size of 1-5 mu m to carry out sand blasting treatment on the surface of the matrix, so that the cleanliness of the surface of the matrix meets the Sa 2.5-3.0 level requirement;
preparing a coating:
and (3) spraying compressed air of 0.8MPa for 2 times under the condition that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protective and energy-saving synergistic coating.
Compared with the prior art, the invention has the following advantages:
1. the spinel high-entropy ceramic and the rare earth oxide added in the invention can be used for double collaborative optimization of the radiation heat transfer of the boiler, and greatly improve the heat exchange efficiency of the boiler.
The spinel high-entropy ceramic has extremely high infrared radiation rate due to the combined action of doping of various transition metal elements and oxygen vacancies in lattice defects. Since the rare earth oxide element contains 4f electrons which are not fully filled, the rare earth oxide element can absorb or emit light with different wavelengths from ultraviolet and visible infrared regions, so that the rare earth oxide element has high infrared radiation rate. In addition, the rare earth oxide has self-diagnosis, self-adjustment, self-repair functions and high-temperature infrared radiation characteristics, is often used as a functional material to optimize the performance of the coating, and is called as an industrial vitamin. The spinel Dan Gaoshang ceramic and the rare earth oxide are used as main raw materials of the coating, so that the infrared emissivity of the coating can be greatly increased under the synergistic effect, and the infrared emissivity of the coating is 0.92-0.95.
The heat transfer is mainly based on infrared radiation, the infrared emissivity of the surface of the original metal heating surface is about 0.7, heat energy generated by combustion of a hearth is radiated to the heating surface in the form of electromagnetic waves, and the metal heating surface absorbs part of the electromagnetic waves and converts the electromagnetic waves into heat energy, so that the surface of the heating surface is heated, and the heat is transferred to an internal low-temperature position. At the same time, a large amount of electromagnetic waves are reflected back to the hearth. After the metal heating surface is reformed by using a coating technology, heat energy is radiated to the surface of the coating in the form of electromagnetic waves, and the coating has extremely high infrared emissivity of 0.92-0.95, so that the electromagnetic waves can be absorbed more effectively and converted into heat energy, the temperature of the surface of the coating is increased rapidly, and the heat energy is transmitted to the metal heating surface and working medium in the metal pipe through the coating, so that the heat exchange efficiency of the boiler is improved greatly.
2. The particle sizes of the surfaces of the coatings are distributed stepwise, so that the risk of coking and slagging of the radiation heating surfaces can be effectively prevented.
The multifunctional protective and energy-saving synergistic coating is composed of a plurality of micro/nano powder materials, and when the content of nano powder is 15-35%, a micro/nano mastoid secondary structure similar to the lotus leaf surface is formed, so that the surface of the coating has the characteristic of step distribution, namely the characteristic of low surface energy; meanwhile, the composite adhesive contains tetraethoxysilane and has the characteristic of low surface energy. When the surface energy of the heating surface is lower than the critical free energy of the molten coke particles, the coke particles cannot adhere to the surface of the heating surface.
Compared with the surface of the original metal pipe wall, the protective and energy-saving synergistic coating has lower surface energy, so that molten coke particles are difficult to adhere to a heating surface, thereby effectively preventing the pollution of the water-cooled wall and reducing coking. Even if a small amount of coking exists, the surface energy of the coating is small, and the coking block exceeds the critical value of adhesive force in a small time and automatically drops off, so that large coking blocks cannot be formed.
In addition, the protective and energy-saving synergistic coating has the function of strengthening radiation, can properly improve the heat absorption capacity of a heating surface, reduce the outlet temperature of a hearth, and can also effectively prevent the coking of a reheater and a superheater.
As shown in fig. 1, the coating obtained by the invention is prepared on a 12Cr1MoVG pipe and cured for 24 hours at room temperature; then, the mixture was cured at 500℃for 6 hours. Finally, the coupon was placed in a coal cinder having an alkali metal content of 44.29% and removed at 600 ℃ for 72 hours, and the coupon surface was observed, showing: no obvious coking phenomenon, and the coating has good coking resistance.
3. The invention adopts the compound of the chromium aluminum phosphate and the tetraethoxysilane as the coating binder, has extremely high temperature resistance, ensures that the use temperature of the coating can reach 1700 ℃, and further ensures that the use range of the coating can be expanded to the surface of a metal heating surface with higher temperature, such as a superheater, a reheater and the like.
4. The coating obtained by the invention has the characteristic of high-temperature corrosion resistance (the use temperature reaches 1700 ℃).
Conventional silicate system coatings, used at temperatures below 1000 ℃, are suitable for use in water wall areas. The binder of the coating is a chromium aluminum phosphate and tetraethoxysilane compound, has extremely high temperature resistance, and the use temperature of the coating can reach 1700 ℃, so that the use range of the coating can be expanded to the surface of a metal heating surface with higher temperature, such as a superheater and a reheater. As shown in FIG. 2, the coating obtained by the invention is prepared on refractory bricks and cured for 24 hours at room temperature; then, the refractory brick was calcined at 1700℃for 48 hours, and the surface of the refractory brick was observed. The results show that the coating has good high temperature resistance, and no obvious phenomena of bubbling, cracking, falling off and the like.
In addition, the use of a composite binder of aluminum chromium phosphate and ethyl orthosilicate can provide a more intimate bond between the coating and the substrate. The compact protective and energy-saving synergistic coating effectively isolates the contact between the metal matrix and the outside, isolates the direct chemical reaction between the molten sulfate and the metal matrix, and simultaneously avoids the reduction corrosive gas H 2 S, CO passes through the protective layer to corrode the metal tube wall, thereby exerting good high-temperature corrosion resistance of the coating. As shown in FIG. 3, the coating sample obtained by the invention is placed in mixed salt of sodium sulfate and potassium chloride in a ratio of 3:1, and calcined at 650 ℃ for 120 hours, and the coating is complete after being taken out, so that the coating has good molten salt corrosion resistance.
5. The coating obtained by the invention has high matching degree of the thermal expansion coefficient with the base material.
The coating adopts spinel high-entropy ceramics, alumina, silicon oxide, cordierite and other raw materials with low thermal expansion coefficients, and the coating and the matrix have matched thermal expansion coefficients by adjusting the percentages of the raw material components, so that the thermal shock resistance is improved. As shown in FIG. 4, the coating obtained by the invention is prepared on a stainless steel sample, and after the temperature is raised by 1000 ℃, the coating is quenched by cold water for 40 times, and the coating does not crack or fall off, and shows good thermal shock resistance.
In addition, the matched thermal expansion coefficient enables the coating to be closely adhered to the surface of the substrate, the coating does not fall off or crack, the substrate is effectively protected, and oxidation, abrasion and high-temperature corrosion of the substrate are prevented.
6. The coatings obtained according to the invention were subjected to performance tests and the results are shown in Table 1.
TABLE 1 Performance index
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows that the multifunctional protective and energy-saving synergistic coating has excellent anti-coking performance. The left graph shows the initial appearance of a 12Cr1MoVG sample tube for preparing the coating, which is placed in coal slag with the content of alkali metal of 44.29 percent; the right panel shows the morphology of the coupon after being maintained in the cinder at 600 c for 72 hours.
FIG. 2 shows the high temperature resistance of the multifunctional protective and energy saving synergistic coating of the present invention.
FIG. 3 illustrates the corrosion resistance of the multi-functional protective and energy-efficient synergistic coating of the present invention.
FIG. 4 illustrates the thermal shock resistance of the multi-functional protective and energy efficient coating of the present invention.
Detailed Description
The multifunctional protective and energy-saving synergistic coating consists of the following raw materials in percentage by weight (g/g): 10-30% of spinel high-entropy ceramic, 2-4% of rare earth oxide, 10-12% of silicon oxide, 8-12% of aluminum oxide, 8-10% of aluminum nitride, 6-8% of cordierite, 3-4% of brown corundum, 0.5-2% of bentonite, 30-40% of composite binder, 0.4-0.6% of dispersing agent and 0.4-0.6% of defoaming agent.
Wherein: the spinel high entropy ceramic is prepared from CuO, mnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 Any six of ZnO and MgO powder are used as raw materials, ball milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in an air atmosphere, and then cooling and grinding are carried out, so that the high-entropy oxide with the spinel structure and the particle size of 300-800 nm is obtained. The preparation method is shown in 202010919577.8, namely a preparation method of an oxide with high solar absorptivity and infrared emissivity.
The rare earth oxide is any 1-2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and the particle size is 0.5-1.0 mu m.
The particle sizes of the silicon oxide and the aluminum oxide are 1 μm; the grain diameter of the aluminum nitride is 200-300 nm; the particle sizes of the cordierite and the bentonite are 10 mu m; the grain size of brown corundum is 1-2 mu m.
The composite binder refers to chromium aluminum phosphate and positive aluminum phosphateEthyl silicate according to 3:1 mass ratio, and stirring and mixing uniformly. Chromium aluminum phosphate (Cr) 2 O 3 ·Al 2 O 3 ·2P 2 O 5 ·6H 2 O) is a double salt composed of chromium phosphate, aluminum phosphate and phosphoric acid provided by Henan Saint New Material technology Co., ltd.
The dispersing agent is one of the following components of the Maier chemical HY-330A+HY-330B, di-high Dispers-760W and Kaimei KMT-3021.
The defoamer is one of Kelmett KMT-2017, digaorex-902W and DigaTego 825.
The thickness of the coating is 100-200 mu m.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing according to a proportion;
preparing a coating:
firstly, dispersing agents and defoaming agents are sequentially added into a composite adhesive and fully stirred; then, adding the spinel Dan Gaoshang ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite in sequence, and dispersing uniformly at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and ball milling at 300-500 rpm for 3-5 hours to obtain a uniform multifunctional protective and energy-saving coating;
thirdly, adopting quartz stone or brown corundum with the particle size of 1-5 mu m to carry out sand blasting treatment on the surface of the matrix, so that the cleanliness of the surface of the matrix meets the Sa 2.5-3.0 level requirement;
preparing a coating:
and (3) spraying compressed air of 0.8MPa for 2 times under the condition that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protective and energy-saving synergistic coating.
The multifunctional protective and energy-saving synergistic coating of the embodiment 1 consists of 10% of spinel high-entropy ceramic, 4% of cerium oxide, 12% of silicon oxide, 12% of aluminum oxide, 10% of aluminum nitride, 6% of cordierite, 3% of brown alumina, 2% of bentonite, 40% of a composite binder, 0.6% of a dispersing agent and 0.4% of a defoaming agent.
Wherein: the dispersant consists of HY-320A: HY-320 b=1: 1 (g/g). The defoaming agent is HY-1040F.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing according to a proportion;
preparing a coating:
firstly, dispersing agents and defoaming agents are sequentially added into a composite adhesive and fully stirred; then, sequentially adding spinel high-entropy ceramic, cerium oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; and finally, transferring the mixture into a ball mill, and ball milling at 300rpm for 5 hours to obtain the uniform multifunctional protective and energy-saving coating.
Thirdly, adopting quartz stone or brown corundum with the particle size of 1-5 mu m to carry out sand blasting treatment on the surface of the substrate, so that the cleanliness of the surface of the substrate meets the Sa 2.5-3.0 level requirement.
Preparing a coating:
and (3) spraying compressed air of 0.8MPa for 2 times under the condition that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protective and energy-saving synergistic coating with the thickness of 100 mu m.
The resulting coating performance index is shown in table 2.
TABLE 2 Performance index
Example 2 a multifunctional protective and energy-saving synergistic coating is composed of 30% of spinel high-entropy ceramic, 1% of yttrium oxide, 2% of dysprosium oxide, 10% of silicon oxide, 8% of aluminum nitride, 6% of cordierite, 3.5% of brown corundum, 0.5% of bentonite, 30% of a composite binder, 0.4% of a dispersing agent and 0.6% of a defoaming agent.
Wherein: the dispersant is Dispers-706W; the defoamer is Airex-902W.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing according to a proportion;
preparing a coating:
firstly, dispersing agents and defoaming agents are sequentially added into a composite adhesive and fully stirred; then, sequentially adding spinel high-entropy ceramic, yttrium oxide, dysprosium oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and dispersing uniformly at a high speed to obtain a mixture; and finally, transferring the mixture into a ball mill, and ball-milling for 3 hours at 300rpm to obtain the uniform multifunctional protective and energy-saving coating.
Thirdly, adopting quartz stone or brown corundum with the particle size of 1-5 mu m to carry out sand blasting treatment on the surface of the substrate, so that the cleanliness of the surface of the substrate meets the Sa 2.5-3.0 level requirement.
Preparing a coating:
and (3) spraying compressed air of 0.8MPa for 2 times under the condition that the ambient temperature is 15-30 ℃ and the air relative humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protective and energy-saving synergistic coating with the thickness of 200 mu m.
The resulting coating performance index is shown in table 3.
TABLE 3 Performance index
Example 3 a multifunctional protective and energy-saving synergistic coating is composed of 18% of spinel high-entropy ceramic, 2% of neodymium oxide, 10% of silicon oxide, 10% of aluminum nitride, 8% of cordierite, 3% of brown alumina, 2% of bentonite, 36% of a composite binder, 0.5% of a dispersing agent and 0.5% of a defoaming agent.
Wherein: the dispersant consists of HY-320A: HY-320 b=1: 1 (g/g). The defoaming agent is HY-1040F.
The preparation method of the multifunctional protective and energy-saving synergistic coating is the same as that of the embodiment 1, wherein neodymium oxide replaces cerium oxide. The thickness of the obtained multifunctional protective and energy-saving synergistic coating is 150 mu m.
The resulting coating performance index is shown in table 4.
TABLE 4 Performance index
Example 4 a multifunctional protective and energy-saving synergistic coating, which consists of 24% of spinel high-entropy ceramic, 1% of yttrium oxide, 2% of lanthanum oxide, 10% of silicon oxide, 8% of aluminum nitride, 6% of cordierite, 4% of brown corundum, 1% of bentonite, 35% of a composite binder, 0.5% of a dispersing agent and 0.5% of a defoaming agent.
Wherein: the dispersant is KMT-3021; the defoamer was Tego825.
The preparation method of the multifunctional protective and energy-saving synergistic coating is the same as that of the embodiment 2, wherein: lanthanum oxide replaces dysprosium oxide. The thickness of the obtained multifunctional protective and energy-saving synergistic coating is 200 mu m.
The resulting coating performance index is shown in table 5.
TABLE 5 Performance index
Claims (2)
1. A multifunctional protective and energy-saving synergistic coating is characterized in that: the coating is prepared from the following raw materials in percentage by weight: 10-30% of spinel high-entropy ceramic, 2-4% of rare earth oxide, 10-12% of silicon oxide, 8-12% of aluminum oxide, 8-10% of aluminum nitride, 6-8% of cordierite, 3-4% of brown corundum, 0.5-2% of bentonite, 30-40% of a composite binder, 0.4-0.6% of a dispersing agent and 0.4-0.6% of a defoaming agent; the spinel high-entropy ceramic is prepared from CuO, mnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 Any six of ZnO and MgO powder are used as raw materials, ball milling, mixing, drying and grinding are carried out, then high-temperature calcination is carried out in an air atmosphere, and then cooling and grinding are carried out, so that the high-entropy oxide with the spinel structure and the grain diameter of 300-800 nm is prepared; the rare earth oxide is any 1-2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and has particle size0.5-1.0 μm; the particle sizes of the silicon oxide and the aluminum oxide are 1 mu m; the grain size of the aluminum nitride is 200-300 nm; the particle sizes of the cordierite and the bentonite are 10 mu m; the grain size of the brown corundum is 1-2 mu m; the composite binder is prepared from chromium aluminum phosphate and ethyl orthosilicate according to a weight ratio of 3:1, uniformly stirring and mixing the compound; the dispersing agent is one of wheat chemical HY-330A+HY-330B, di-high Dispers-760W and Kaimei KMT-3021; the defoamer is one of Kelmett KMT-2017, digaorex-902W and DigaTego 825; the preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing according to a proportion;
preparing a coating:
firstly, dispersing agents and defoaming agents are sequentially added into a composite adhesive and fully stirred; then, adding the spinel Dan Gaoshang ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite in sequence, and dispersing uniformly at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and ball milling at 300-500 rpm for 3-5 hours to obtain a uniform multifunctional protective and energy-saving coating;
thirdly, adopting quartz stone or brown corundum with the particle size of 1-5 mu m to carry out sand blasting treatment on the surface of the matrix, so that the cleanliness of the surface of the matrix meets the Sa 2.5-3.0 level requirement;
preparing a coating:
and (3) spraying compressed air of 0.8MPa for 2 times under the condition that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protective and energy-saving synergistic coating.
2. A multi-functional protective and energy-efficient synergistic coating as claimed in claim 1, characterized in that: the thickness of the coating is 100-200 mu m.
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