CN112517354A - Super-amphiphobic composite coating on heat exchange tube, preparation process thereof and flue gas heat exchange device based on super-amphiphobic composite coating - Google Patents
Super-amphiphobic composite coating on heat exchange tube, preparation process thereof and flue gas heat exchange device based on super-amphiphobic composite coating Download PDFInfo
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- CN112517354A CN112517354A CN202011315368.9A CN202011315368A CN112517354A CN 112517354 A CN112517354 A CN 112517354A CN 202011315368 A CN202011315368 A CN 202011315368A CN 112517354 A CN112517354 A CN 112517354A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 87
- 238000000576 coating method Methods 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 26
- 238000005488 sandblasting Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 13
- 238000004939 coking Methods 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000008719 thickening Effects 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 4
- 238000005536 corrosion prevention Methods 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 239000003245 coal Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/582—No clear coat specified all layers being cured or baked together
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F1/00—Tubular elements; Assemblies of tubular elements
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/04—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/22—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/08—Coatings; Surface treatments self-cleaning
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a super-amphiphobic composite coating on a heat exchange tube, a preparation process thereof and a flue gas heat exchange device based on the super-amphiphobic composite coating, and belongs to the technical field of corrosion prevention and coking prevention of heat exchange tubes of flue gas heat exchangers. And removing impurities on the surface of the heat exchange tube by using hydrochloric acid, neutralizing acid liquor remained on the surface, further performing sand blasting treatment to increase the adhesive force of the coating, and facilitating later-stage coating spraying, wherein the first primer layer is used for further increasing the adhesive force of the coating and facilitating the adhesion of the second composite coating. The combination of special heat exchange tube arrangement, thickened tube wall and the construction of nano-microstructure composite self-cleaning surface coating is adopted, so that the corrosion resistance and self-cleaning performance of the heat exchange tube are improved, and the times of cleaning and replacing the heat exchange tube are reduced. The combination of the three components is superior to the single use of the heat exchange tube arrangement, the thickening of the tube wall and the construction of the nano-micro structure composite self-cleaning surface coating.
Description
Technical Field
The invention belongs to the technical field of corrosion prevention and coking prevention of heat exchange tubes of flue gas heat exchangers, and relates to a super-amphiphobic composite coating on a heat exchange tube, a preparation process of the super-amphiphobic composite coating and a flue gas heat exchange device based on the super-amphiphobic composite coating.
Background
Coal is an important primary energy source in China at present, a key technology for low-rank coal quality-based utilization and industrialization of the low-rank coal quality-based utilization have important influence on coal utilization, and a medium-low temperature carbonization technology is called as a 'tap' for coal quality-based graded utilization. The semi-coke industry is derived in the coal quality-based utilization process. The flue gas that produces in the blue charcoal production process contains a large amount of acid gas and dust, and acid gas can aggravate the corruption of heat exchanger, and the dust can increase heat exchanger heat transfer resistance, thereby makes the heat transfer performance of heat exchanger reduce by a wide margin based on the problem in above two aspects, and waste heat is white extravagant even, causes the waste of the energy.
In the flue gas waste heat exchanger, flue gas passes through a shell pass, air passes through a tube pass, the flue gas waste heat is used for heating air, and preheated air can be used as a raw material for low-temperature carbonization of coal. The flue gas enters from the top through the heat exchange tube and is discharged from the bottom, the temperature of the heat exchange tube at the bottom is lowest, the water vapor is most easily condensed, and SO in the smoke dust is2、S03Sulfuric acid is generated when the water meets the requirement, and the outer wall of the heat exchange tube is seriously corroded. In the process of temperature reduction, a small amount of coal tar vapor in the flue gas is also condensed into coal tar and is combined with coal dust to form a coking material. In addition, from the viewpoint of environmental protection, the temperature of the flue gas must be reduced to below 200 ℃ for bag-type dust removal. The acid gas in the flue gas easily corrodes the heat exchange tube, even if the high-price 316L steel is adopted, the heat exchange tube can only be maintained and replaced after being used for 2-3 months, and the process discontinuity and the discontinuous supply of hot air are inevitably caused by the shutdown replacement and the maintenance.
Therefore, the method has great practical significance for factories to solve the problem of difficulty in corrosion prevention and coking prevention of the heat exchanger in semi-coke production.
Disclosure of Invention
The invention aims to overcome the defects that a heat exchanger is easy to corrode and coke in semi coke production in the prior art, and provides a super-amphiphobic composite coating on a heat exchange tube, a preparation process thereof and a flue gas heat exchange device based on the super-amphiphobic composite coating.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation process of a super-amphiphobic composite coating on a heat exchange tube comprises the following steps:
1) placing the heat exchange tube into 0.5-1.0 mol/L HCl solution, soaking for 1-1.5 h, washing with alkali liquor to be neutral, washing with clear water, drying, and performing sand blasting treatment on the surface of the heat exchange tube;
2) uniformly spraying fluorine-containing paint on the surface of a heat exchange tube to form a first coating with the thickness of 20-50 mu m;
3) adding an ethylene-tetrafluoroethylene copolymer into ethyl acetate, carrying out ultrasonic stirring for 20-30 min, sequentially adding ZnO nanoparticles, polyaniline and carbon nanotube particles to obtain a mixed solution, carrying out ultrasonic stirring for 1-3 h, adding perfluorooctyl triethoxysilane, continuing to carry out ultrasonic stirring for 0.5-1.0 h to obtain a second coating solution, and spraying the second coating solution on the first coating obtained in the step 2) to obtain a second coating; then uniformly spraying SiO on the second coating2Nano particles to obtain a composite coating; wherein, the ethylene-tetrafluoroethyleneCopolymer, perfluorooctyltriethoxysilane, SiO2The feeding ratio of the nano particles, the ZnO nano particles, the polyaniline, the carbon nano tubes and the ethyl acetate is 30 g: 9 ml: 5 g: 5 g: 1 g: 3 g: 900 ml;
4) and 3) placing the heat exchange tube treated in the step 3) at 100-240 ℃ for gradient baking for 12-16 h, and cooling to room temperature to obtain the super-amphiphobic composite coating on the surface of the heat exchange tube.
Preferably, the drying of step 1) is carried out in a nitrogen atmosphere; the method also comprises the step of roughening the surface of the heat exchange pipe after the sand blasting treatment in the step 1).
Preferably, the fluorine-containing primer is a resin based on an ethylene-tetrafluoroethylene copolymer, wherein the fluorine content in the fluorine-containing primer is 35%.
Preferably, the spraying is electrostatic; the spraying in the step 2) is carried out under 0.5-1.5 MPa; and 3) spraying at 3-8 bar.
Preferably, the gradient baking in step 4) is specifically: the heat exchange tube treated in the step 3) is placed at 100 ℃ for baking for 8-9 h, at 140 ℃ for baking for 1-2 h, at 180 ℃ for baking for 1-2 h, at 220 ℃ for baking for 1-2 h, and at 240 ℃ for standing for 1-2 h.
The heat exchange tube with the super-amphiphobic composite coating is obtained based on the preparation process, and the contact angles of the super-amphiphobic composite coating to an ethanol aqueous solution and concentrated sulfuric acid are respectively up to 149 degrees and 143 degrees.
Preferably, the heat exchange tube is made of a galvanized tube.
Preferably, the thickness of the super-amphiphobic composite coating is 50-100 μm.
The utility model provides a flue gas heat transfer device of heat exchange tube, the thickness of heat exchange tube is 2.2 ~ 2.8 mm.
Preferably, a coke collecting tank is arranged at the bottom of the heat exchange tube.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation process of a super-amphiphobic composite coating, which is characterized in that impurities on the surface of a heat exchange tube are removed by hydrochloric acid, then acid liquor remained on the surface is neutralized, the adhesion of the coating is increased by further sand blasting treatment, the later-stage coating spraying is facilitated, the first layer of primer is used for further increasing the adhesion of the coating, and the adhesion of the second layer of composite coating is facilitated. The coating with the self-cleaning function can effectively reduce the formation of coked materials and the thermal resistance of dirt, and the arrangement of the heat exchange tubes in a dense mode can ensure the heat transfer effect, reduce the number of the heat exchange tubes and reduce the cost.
The invention also discloses a heat exchange tube with the super-amphiphobic composite coating, and the cross adhesive tape test result shows that the super-amphiphobic composite coating has good adhesive force, shows good stability in acid-base salt and organic solution, and has excellent self-cleaning and antifouling properties on ethanol and concentrated sulfuric acid sludge.
The invention also discloses a flue gas heat exchange device which is built based on the heat exchange tubes, the arrangement of the heat exchange tubes is reasonably improved, and the heat exchange tubes are sparsely arranged at the bottom end of an inlet with the most serious corrosion, SO that the water vapor in the flue gas is ensured not to be condensed in the production process, and the SO in the flue gas is ensured to be condensed2、S03Sulfuric acid is not generated when the water is in contact with the water, so that the corrosion of the heat exchange tube is greatly reduced. The combination of special heat exchange tube arrangement, thickened tube wall and the construction of nano-microstructure composite self-cleaning surface coating is adopted, so that the corrosion resistance and self-cleaning performance of the heat exchange tube are improved, and the times of cleaning and replacing the heat exchange tube are reduced. The combination of the three components is superior to the single use of the heat exchange tube arrangement, the thickening of the tube wall and the construction of the nano-micro structure composite self-cleaning surface coating.
Furthermore, the corrosion resistance of the heat exchange tube can be improved by thickening the tube wall of the heat exchange tube.
Furthermore, a coking material collecting tank is arranged at the bottom of the heat exchange tube, so that the heat exchange tube is convenient to clean, and the problem of coking and blockage of subsequent pipeline equipment can be reduced.
Furthermore, the bottom heat exchange tube of the heat exchanger is most easily corroded, and the heat exchange tubes are arranged sparsely, SO that water vapor is not easy to condense, and SO in smoke dust is not easy to condense2、S03Sulfuric acid can not be generated, thereby effectively reducing the corrosion of the heat exchange tube.
Drawings
FIG. 1 is an arrangement view of a heat exchange tube in the prior art;
FIG. 2 is an arrangement view of heat exchange tubes in the flue gas heat exchange device of the present invention;
FIG. 3 is a full cross-sectional view of a prior art heat exchange tube;
FIG. 4 is a full sectional view of the heat exchange tube in the flue gas heat exchange device of the present invention;
FIG. 5 is a coke thickness comparison of the heat exchange tubes of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is described in further detail below with reference to the accompanying drawings:
the corrosion and coking problems of the heat exchange tubes in the flue gas heat exchanger are serious, particularly, the heat exchange tubes at the bottom end are corroded most seriously, the coking materials are adhered very tightly, the heat exchange tubes are arranged in a staggered square mode, the density is high, only the heat transfer effect is considered, the actual facing condition of the flue gas waste heat exchanger is ignored, after coking, great difficulty is brought to workers to clean the flue gas waste heat exchanger, and the normal blue charcoal production of a factory is delayed. In consideration of the factors, on the basis of adopting square staggered arrangement on a large area, a sparser regular triangle arrangement is adopted near the bottom end of the heat exchanger. Therefore, the temperature of the flue gas outlet can be guaranteed to be higher than the condensation temperature of water vapor, and the corrosion is effectively slowed down. In the actual semi-coke production process, as heat exchanger equipment needs excellent heat transfer performance and great processing capacity, 942 improved front heat exchanger heat exchange tubes and 899 improved rear heat exchanger heat exchange tubes are arranged, and a diagram (1) and a diagram (2) are respectively a diagram of arrangement of an original integral heat exchange tube arrangement and a diagram of arrangement after improvement. In order to enhance the corrosion resistance of the heat exchange tube, the wall of the common heat exchange tube with the thickness of 2mm is increased to the heat exchange tube with the thickness of 2.5 mm. FIG. 3 is a full sectional view of the original heat exchange tube. Fig. 4 is a sectional view of the improved heat exchange tube wall and the structure thereof. The shell, the pipe fitting and other surfaces exposed on the shell pass need to be treated, the corrosion resistance and the coking resistance are enhanced, and a composite coating with good performance is adopted. The coating must satisfy adhesion, high temperature resistance and corrosion resistance.
Preparation of super-amphiphobic composite coating
Example 1
(1) Putting the heat exchange tube into 0.5mol/L HCl solution, soaking and washing for 1.5h, neutralizing with alkaline solution, washing for 3 times with tap water until neutralization, and drying in nitrogen atmosphere;
(2) placing the outer surface of the heat exchange tube and the inner surface of the shell under a high-speed sand blasting machine, performing sand blasting treatment to remove surface impurities, and simultaneously performing roughening treatment on the surface;
(3) uniformly spraying fluorine-containing paint on the outer surface of the heat exchange tube and the inner surface of the shell under 0.5MPa, wherein the spraying thickness is 20 mu m, and the adhesive force is enhanced; the fluorine-containing primer is resin based on ethylene-tetrafluoroethylene copolymer, wherein the fluorine content in the fluorine-containing primer is 35 percent;
(4) adding 3g of ethylene-tetrafluoroethylene copolymer into 90ml of ethyl acetate, ultrasonically stirring for 20min, sequentially adding 0.5g of ZnO nano particles, 0.1g of polyaniline and 0.3g of carbon nano tube particles to obtain a mixed solution, ultrasonically stirring for 3h, adding 0.9ml of perfluorooctyltriethoxysilane, continuously ultrasonically stirring for 1h to obtain a second coating solution, uniformly spraying the mixed solution on the surface with a first coating (namely a primer) by using a spray gun at the pressure of 8bar to form a coating with the thickness of 50 mu m, and uniformly spraying 0.5g of SiO on the second coating2Nano particles to obtain a composite coating with the total thickness of 50 mu m;
(5) and (3) baking the composite coating at 100 ℃ for 9h, 140 ℃ for 2h, 180 ℃ for 2h, 220 ℃ for 2h, 240 ℃ for 2h, performing gradient solidification, and naturally cooling to obtain the super-amphiphobic coating.
Example 2
(1) Putting the heat exchange tube into 1.0mol/L HCl solution, soaking and washing for 1h, neutralizing with alkali liquor, washing for 3 times with tap water until neutralization, and drying in nitrogen atmosphere;
(2) placing the outer surface of the heat exchange tube and the inner surface of the shell under a high-speed sand blasting machine, performing sand blasting treatment to remove surface impurities, and simultaneously performing roughening treatment on the surface;
(3) uniformly spraying fluorine-containing paint on the outer surface of the heat exchange tube and the inner surface of the shell under 1.5MPa, wherein the spraying thickness is 30 mu m, and the adhesive force is enhanced; the fluorine-containing primer is resin based on ethylene-tetrafluoroethylene copolymer, wherein the fluorine content in the fluorine-containing primer is 35 percent;
(4) adding 0.3g of ethylene-tetrafluoroethylene copolymer into 9ml of ethyl acetate, ultrasonically stirring for 20min, sequentially adding 0.05g of ZnO nanoparticles, 0.01g of polyaniline and 0.03g of carbon nanotube particles to obtain a mixed solution, ultrasonically stirring for 1h, adding 0.09ml of perfluorooctyltriethoxysilane, continuously ultrasonically stirring for 0.5h to obtain a second coating solution, uniformly spraying the mixed solution on the surface with a first coating (namely a primer) by using a spray gun at the pressure of 5bar to form a coating with the thickness of 50 mu m, and uniformly spraying 0.5g of SiO on the second coating2Nano particles to obtain a composite coating with the total thickness of 50 mu m;
(5) and (3) baking the composite coating at 100 ℃ for 8h, 140 ℃ for 1h, 180 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h, performing gradient solidification, and naturally cooling to obtain the super-amphiphobic coating.
Example 3
(1) Putting the heat exchange tube into 0.7mol/L HCl solution, soaking and washing for 1h, neutralizing with alkali liquor, washing for 3 times with tap water until neutralization, and drying in nitrogen atmosphere;
(2) placing the outer surface of the heat exchange tube and the inner surface of the shell under a high-speed sand blasting machine, performing sand blasting treatment to remove surface impurities, and simultaneously performing roughening treatment on the surface;
(3) uniformly spraying fluorine-containing paint on the outer surface of the heat exchange tube and the inner surface of the shell under 1.0MPa, wherein the spraying thickness is 25 mu m, and the adhesive force is enhanced; the fluorine-containing primer is resin based on ethylene-tetrafluoroethylene copolymer, wherein the fluorine content in the fluorine-containing primer is 35 percent;
(4) 0.6g of ethylene-tetrafluoroethylene copolymer was added to 18ml of ethyl acetate, and the mixture was ultrasonically stirred for 30 minutesmin, sequentially adding 0.1g of ZnO nanoparticles, 0.02g of polyaniline and 0.06g of carbon nanotube particles to obtain a mixed solution, ultrasonically stirring for 1h, adding 0.18ml of perfluorooctyl triethoxysilane, continuously ultrasonically stirring for 1.0h to obtain a second coating solution, uniformly spraying the mixed solution on the surface with the first coating (i.e. the primer) by using a spray gun at the pressure of 3bar, and uniformly spraying 0.1g of SiO on the second coating2Nano particles to obtain a composite coating with the total thickness of 50 mu m;
(5) and (3) baking the composite coating at 100 ℃ for 8h, 140 ℃ for 1h, 180 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h, performing gradient solidification, and naturally cooling to obtain the super-amphiphobic coating.
The super-amphiphobic composite coating on the surface of the heat exchange tube prepared in the example 1 is subjected to a performance test, and the contact angles of the coating to an ethanol water solution and concentrated sulfuric acid are respectively up to 149 degrees and 143 degrees.
And performing a cross adhesive tape test on the composite coating by using GB/T9286, evaluating the adhesive force of the coating, scratching the coating into squares by using a wallpaper knife until the metal substrate is exposed, pressing the sample by using an adhesive tape for 2min, tearing the sample, repeating the process for multiple times, wherein the substrate is not found to fall off on the surface of the adhesive tape, and the adhesive force of the coating is good.
Selecting CH with mass concentration of 10%3COOH solution, NaOH solution, NaCl solution and CH3COCH3The solution is used as a simulation material to respectively simulate the acid-base salt and organic solution environments faced by the coating, the tinplate coating sample plate prepared by the method is respectively soaked in the solution, the change of the antenna of the modified sample plate is measured every day, and the contact angle of the sample plate is not changed greatly after the sample plate is soaked in the four solutions for six days, so that the coating has better stability in the acid-base salt and organic solution.
The coating has excellent self-cleaning and antifouling properties on both ethanol and concentrated sulfuric acid sludge.
Application example
The effect of the heat exchange tube which is combined by arranging special heat exchange tubes, thickening the tube wall and constructing the nano-microstructure composite self-cleaning surface coating is compared with that of the original heat exchange tube, the arrangement mode of the original heat exchange tube is shown in figures 1 and 3, and the arrangement of the heat exchange tube is shown in figures 2 and 4. In the invention, the number of the heat exchange tubes is changed from 942 to 899, the tube wall is changed from 2mm to 2.5mm, and the surface of the heat exchange tube adopts a super-amphiphobic composite coating.
The performance of the improved heat exchanger is analyzed and evaluated by analyzing the relationship between the thickness of the coking material and the time, python mapping is applied, and the result is shown in a graph (5), so that the heat exchange tube combined with the arrangement of the improved special heat exchange tubes, the thickening of the tube wall and the construction of the nano-microstructure composite self-cleaning surface coating is better than the original performance in the aspect of corrosion resistance and coking resistance, the heat exchange tubes are replaced once in two months in the prior art, and the heat exchanger can be cleaned once in one year at present, which is a great progress in the aspect of corrosion resistance and coking resistance of the heat exchanger, so that the improved scheme is proved to be feasible.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation process of a super-amphiphobic composite coating on a heat exchange tube is characterized by comprising the following steps:
1) placing the heat exchange tube into 0.5-1.0 mol/L HCl solution, soaking for 1-1.5 h, washing with alkali liquor to be neutral, washing with clear water, drying, and performing sand blasting treatment on the surface of the heat exchange tube;
2) uniformly spraying fluorine-containing paint on the surface of a heat exchange tube to form a first coating with the thickness of 20-50 mu m;
3) adding an ethylene-tetrafluoroethylene copolymer into ethyl acetate, carrying out ultrasonic stirring for 20-30 min, sequentially adding ZnO nanoparticles, polyaniline and carbon nanotube particles to obtain a mixed solution, carrying out ultrasonic stirring for 1-3 h, adding perfluorooctyl triethoxysilane, continuing to carry out ultrasonic stirring for 0.5-1.0 h to obtain a second coating solution, and spraying the second coating solution on the first coating obtained in the step 2) to obtain a second coating; then uniformly spraying SiO on the second coating2Nanoparticles to obtain a composite coating(ii) a Wherein, the ethylene-tetrafluoroethylene copolymer, the perfluorooctyl triethoxysilane and the SiO2The feeding ratio of the nano particles, the ZnO nano particles, the polyaniline, the carbon nano tubes and the ethyl acetate is 30 g: 9 ml: 5 g: 5 g: 1 g: 3 g: 900 ml;
4) and 3) placing the heat exchange tube treated in the step 3) at 100-240 ℃ for gradient baking for 12-16 h, and cooling to room temperature to obtain the super-amphiphobic composite coating on the surface of the heat exchange tube.
2. The process according to claim 1, wherein the drying of step 1) is carried out in a nitrogen atmosphere; the method also comprises the step of roughening the surface of the heat exchange pipe after the sand blasting treatment in the step 1).
3. The process according to claim 1, wherein the fluorine-containing primer is a resin based on an ethylene-tetrafluoroethylene copolymer, and the fluorine content in the fluorine-containing primer is 35%.
4. The process according to claim 1, wherein the spraying is electrostatic; the spraying in the step 2) is carried out under 0.5-1.5 MPa; and 3) spraying at 3-8 bar.
5. The preparation process according to claim 1, wherein the gradient baking in step 4) is specifically: the heat exchange tube treated in the step 3) is placed at 100 ℃ for baking for 8-9 h, at 140 ℃ for baking for 1-2 h, at 180 ℃ for baking for 1-2 h, at 220 ℃ for baking for 1-2 h, and at 240 ℃ for standing for 1-2 h.
6. A heat exchange tube with a super-amphiphobic composite coating obtained based on the preparation process of any one of claims 1-5 is characterized in that the contact angles of the super-amphiphobic composite coating to an ethanol aqueous solution and concentrated sulfuric acid are respectively up to 149 degrees and 143 degrees.
7. The heat exchange tube of claim 6, wherein the heat exchange tube is made of a galvanized tube.
8. The heat exchange tube of claim 6, wherein the super-amphiphobic composite coating has a thickness of 50-100 μ ι η.
9. A flue gas heat exchange device based on the heat exchange tube of claim 8, wherein the thickness of the heat exchange tube is 2.2-2.8 mm.
10. The flue gas heat exchange device of claim 9, wherein a coke collecting tank is installed at the bottom of the heat exchange tube.
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