CN109897532A - A kind of graphene coating material and preparation method thereof protected in advance for four main tubes of boiler high temperature corrosion - Google Patents
A kind of graphene coating material and preparation method thereof protected in advance for four main tubes of boiler high temperature corrosion Download PDFInfo
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Abstract
The invention discloses a kind of graphene coating materials and preparation method thereof protected in advance for four main tubes of boiler high temperature corrosion, the coating material is by mass percentage, including component: high temperature resistant adhesive 30~65%, nano material dispersion pulp 1~10%, Scale filler 5~20%, flake nano material 1~5%, Heatproof anticorrosion pigment 5~30%, anti-settling agent 0.5~5%, water 0~50%；The coating material is prepared using special preparation method, and homogenize more preferable and stable storage；The coating material not only has excellent high temperature resistance, and coating material is fine and close, has good etch resistant properties to corrosive environment, and have good bonding adhesive force to metal base；In addition, the construction method of the coating material is easy quickly, project cost can be significantly reduced.
Description
Technical field
The present invention relates to coating material technical field more particularly to a kind of stones protected in advance for four main tubes of boiler high temperature corrosion
Black ene coatings material and preparation method thereof.
Background technique
It is always to influence that power plant boiler four, which manages (water screen tube, economizer tube, superheater tube, reheater tube) explosion problem,
Power plant safety, stable electric generation and one of the main reason for cause huge economic losses.According to statistics, non-due to caused by four pipe explosions
Planned outage accident accounts for 60% or more of power plant whole unplanned outage.
Previous the main reason for largely research work thinks booster more, runs for tubing short-term over-temperature and overheat of exceeding the time limit, with
And inside burner hearth caused by the corrosive environment corrosion of complexity.In view of the above-mentioned problems, its settling mode is as follows: one, improving the resistance to of steel pipe
Hot grade improves oxidation-resistance property and improves tubing structure stability, replaces the heat resisting pipe of greater degree.But when use
After temperature reaches 620 DEG C or more, it is extremely limited for further improving the calorific intensity of tubing, and cost can be mentioned significantly
It is high.Two, erosion shield is coated.
The composition of boiler internal corrosion atmosphere is complex and be always in upset condition, but corrosive environment on the whole
Composition has sulfide, sulfate, reducibility gas and chloride etc..Through test and the study found that China's many uses different coals
All there are four different degrees of pipe high temperature corrosion phenomenons in the boiler of kind or coal dust.The sulphur that coal dust wherein contains in burning is by multiple
Miscellaneous changeable process can generate the sulphur of a certain amount of atom free state: [S], these free sulphur atoms can be sent out at high temperature with iron
It is for sulfide corrosion that raw reaction, which generates iron sulfide to cause to corrode to tube wall,.Sulphate corrosion is the ash after coal combustion
In alkali metal oxide be deposited on water cooling tube wall surface, reacting with the sulfur oxide generated after burning, (catalyst is
The oxide of iron), generate sulfate and pyrosulfate, the sulfate and pyrosulfate then generated again with iron, aluminium or iron,
The oxide of aluminium reacts, and generates the composite sulfurs hydrochlorates such as three sulfuric acid ferrisodiums.These reactions can carry out rapidly under the conditions of liquid, right
Tube wall generates serious corrosion.Reducibility gas corrosion is in the ventilation lower boiler of in bad order or air pressure, because oxygen contains
The phenomenon that amount is insufficient, has incomplete combustion or ischaemia.At this point, environment representation be reproducibility, reducibility gas (CO,
H2、CH4) account for relatively high, under the conditions of certain burner hearth, it can react with iron oxide by the reducibility gas of representative of CO, it will
This layer of fine and close protective film is reduced into sparse porous ferrous oxide, at this point, the corrosive mediums such as sulphur, hydrogen sulfide can be easier
Penetrate ferrous oxide, substrate metal is caused to corrode, and corrosion rate can be greatly speeded up.Sodium chloride in coal is after coal combustion
In gaseous state, it can react with sulfur dioxide, silica and generate hydrogen chloride, it can be rapid with the iron oxide in metallic walls
The boiling point of the chloride of reaction generation iron, iron chloride and frerrous chloride is very low, at high temperature highly volatile, so that oxidation film be made to meet with
To destruction.After losing oxidation film, exposed metal pipe-wall is for chloride corrosion by the easier hydrogen-type corrosion that cures.
Currently, solving High Temperature Corrosion generally uses high-temperature resistant anti-corrosive erosion resisting coating.High-temperature resistant anti-corrosive erosion resisting coating is specific
It is divided into organic type coating and inorganic type coating, it is generally the case that the antiseptic property of organic coating is preferable and heat resistance is lower, such as
Patent CN 102190940A, heat resistance can only achieve 500 DEG C, when being applied to four main tubes of boiler, the heat-resistant limit of the coating without
Method reaches requirement, after the long period, with the charing of organic components, the compactness degradation of coating, anti-corrosion
Corrosion can also wretched insufficiency therewith；Inorganic type coating can be subdivided into thermal spraying alloy coating and inorganic ceramic coating again, now answer
With it is most commonly used be thermal spraying alloy coating technology, but actual engineer application shows thermal spraying alloy coating technology not
It can be fully solved such etching problem, the anticorrosion service life short (usual less than one boiler maintenance period) is its maximum deficiency,
The reason for this is that: one, the ingredient of alloy coat be generally nickel, chromium, titanium, aluminium etc., their anticorrosion mechanisms in corrosive environment are sacrificial
Domestic animal property anti-corrosion, with the extension of etching time, coating is thinned, ultimate failure；Two, alloy coat is difficult to after spraying forms coating
The meeting avoided is even more that not can avoid there are the presence of a large amount of hole and crackle, especially hole, can not completely cut off corrosion completely
Atmosphere, corrosive environment can go directly four main tubes of boiler directly through alloy coat, as time went on, corrode the layer in alloy coat
Lower sprawling causes alloy coat to lose attachment so that falling off, to lose protection effect.In addition its complicated construction technology and compared with
Long construction period cause makes it have high project cost, and such as 104264102 B of patent CN, the alloy clearly proposed is applied
The pore problem of layer, and the seal coat used in it is organic silicon coating, the heat resistance of organic silicon coating as previously mentioned, there are
Great drawback；Inorganic ceramic coating is above subject to certain restrictions due to sintering curing temperature drift in application, such as Deutsche Bundespatent
CN100354455C, sintering temperature is at 1000 DEG C, in large-area construction using upper, especially in boiler water wall using upper logical
It crosses and is sintered with the mode of furnace heating, complicated component in it when due to boiler combustion, coal dust, air including larger flow velocity, flue gas,
Dust, lime-ash etc., be it is not fully sintered before can destroy the coating bonded with uncured type binder, to exist apparent anti-
Corrode weak area, in addition, the temperature of furnace wall cooling generally between 500 DEG C to 600 DEG C, and its excessively high sintering temperature is (most
Low 1000 DEG C) it is extremely difficult to.
Therefore, in view of the above-mentioned problems, it is necessary to develop suitable for above-mentioned high-temperature corrosion environment and easy construction it is new
Coating protection system.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, it is pre- for four main tubes of boiler high temperature corrosion that the purpose of the present invention is to provide one kind
Graphene coating material of protection and preparation method thereof, it is intended to which it is short to solve the existing alloy coating material anticorrosion service life, construction
The higher problem of project cost.The coating material not only has excellent high temperature resistance, and coating material is fine and close, to corrosive environment
There is good bonding adhesive force with good etch resistant properties, and to metal base.In addition, the construction party of the coating material
Method is easy quickly, can significantly reduce project cost.The present invention also provides a kind of high temperature resistant graphite for four main tubes of boiler
The preparation method of alkene anticorrosion coating material, preparation method is simple, easy to promote and utilize.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of graphene coating material protected in advance for four main tubes of boiler high temperature corrosion, by mass percentage, including group
Point:
Wherein, the nano material dispersion pulp is to be wrapped by the organic compound containing functional group to nano-powder
Cover the composition formed after processing.
The high temperature resistant adhesive is dihydric phosphate, alkali silicate, the poly- silicon prepared by sol-gel method
At least one of oxygen alkane resin, glass powder.
Wherein, the polyorganosiloxane resin prepared by sol-gel method needs complete hydrolysis, substantially completely to remove
Organic components are removed, and are aided with the coalescing agent of high temperature resistant inorganic type, to ensure the heat resistance of polyorganosiloxane resin.Due to poly-
Organic components in silicone resin are hydrolyzed into methanol or ethyl alcohol, to become decentralized medium, resin body becomes can be resistant to
By the nanometer grade silica aggregate particle of high temperature, this solid point that will lead to resin is reduced, and causes the film forming of resin
It can decline, make to have compounded the inorganic coalescing agent for being resistant to high temperature auxiliary film forming, there is polyorganosiloxane resin good
Filming performance.
Wherein, the glass powder be glass powder with low melting point, melting range be 400~600 DEG C, preferably 500~550
℃。
Wherein its content is preferably 40~55% to high temperature resistant binder by mass percentage.
The high temperature resistant graphene anticorrosion coating material for four main tubes of boiler, which is characterized in that by nano material point
Slurry mass percent meter is dissipated, the nano material dispersion pulp includes component:
Nano material 0.1~20%, preferably 10~20%
Dispersing agent 0.1~20%, preferably 10~20%
Water 60~99.8%, preferably 60~80%；
Wherein, the nano material, particle size are 10nm~500nm, preferably 10nm~100nm.It is being used for pot
The mass percentage of nano material dispersion pulp in the high temperature resistant graphene anticorrosion coating material of four pipe of furnace is preferably 5~
10%.
The nano material includes nano silica, nano aluminium oxide, nano-titanium dioxide, nano titanium powder, nanometer
At least one of nickel powder, nanometer chromium powder, nanometer niobium powder, nanometer aluminium powder, nano zinc powder, when to be a variety of, by any quality hundred
Divide than mixing.
The dispersing agent is the organic compound containing functional group, such as 3- aminopropyl triethoxysilane, γ-(2,3-
The third oxygen of epoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, ethyl orthosilicate, metatitanic acid just
At least one of butyl ester, zirconium-n-butylate, aluminium isopropoxide are mixed when to be a variety of by any mass percent.
The preparation method of the nano material dispersion pulp is that part water and nano material is taken to stir evenly, and in stirring bar
It is gradually warming up to 40 DEG C to 90 DEG C under part, after dropwise addition addition dispersing agent is stirred to react 1h to 2h, moisture is supplied, after cooling down completely
Filtering and discharging obtains nano material dispersion pulp.
The Scale filler is at least one of crystalline flake graphite, mica sheet, when for two kinds, by any mass percent
Mixing, the mass percentage of Scale filler is preferably 15%~25%.The Heatproof anticorrosion pigment is trbasic zinc phosphate, polyphosphoric acids
At least one of aluminium, zinc oxide are mixed, the quality percentage of Heatproof anticorrosion pigment when to be a variety of by any mass percent
Content is preferably 15%~25%.
The anti-settling agent is at least one of rectorite, bentonite, cellulose, when to be a variety of, by any quality hundred
Divide than mixing, the mass percentage of anti-settling agent is preferably 1%~2.5%.
The invention also discloses a kind of preparation sides of graphene coating material protected in advance for four main tubes of boiler high temperature corrosion
Method includes the following steps:
High temperature resistant adhesive, Heatproof anticorrosion pigment and anti-settling agent are proportionally added into decentralized medium, with linear velocity 1~
5m/s stirs 10~30min, and mixing speed is preferably 1~3m/s, is ground to fineness≤40 μm after mixing evenly, and it is mixed to obtain first
Close material；
Scale filler, nano material dispersion pulp and/or flake nano material graphene are proportionally added into the first mixing
In material, filtering and discharging, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler after mixing evenly.
Compared with the existing technology, the graphene coating material protected in advance for four main tubes of boiler high temperature corrosion of the invention has
Following advantage:
It (1) is that powder thermospraying mode forms protective coating compared to four pipe corrosion-inhibiting coating of conventional boiler, in the present invention
High-temperature resistant anti-corrosive coating material is liquid, is constructed using aerial spraying mode, easy to operate, less energy consumption drops project amount significantly
It is low, save construction cost.
(2) anti-corrosion capability is outstanding, by introducing nano material dispersion pulp in coating material, has obtained coating not only
There is excellent high temperature resistance, coating material is fine and close, has good etch resistant properties to corrosive environment.
(3) there is good bonding adhesive force to metal base, covalent bond can be formed with metal base by the way that introducing is a variety of
Material, the modification to high temperature resistant binder so that binder to metal base have good adhesive force.
(4) good with the thermal matching of metal base, pass through addition nano metal powder and other inorganic material powders
Collocation, make coating have with thermal expansion coefficient similar in metal base, be that there is good thermal matching with the coating and steel.
Detailed description of the invention
Fig. 1 is preparation method flow chart of the present invention.
Specific embodiment
Substance provided by the present invention can be synthesized by marketable material or traditional chemical transform mode.Of the invention other
Aspect is obvious to those skilled in the art due to this disclosure.
Below in conjunction with specific embodiment, where specifically disclosing essence of the invention, but should not be understood as can to the present invention
Any restriction of practical range can have different change and modification on the basis of not departing from the connotation.Unless otherwise
Definition or explanation, all professions used herein and scientific words and meaning phase known to those skilled in the art
Together.Furthermore any method similar to or equal to what is recorded and material all can be applied in method of the invention.
Embodiment 1:
Raw material proportioning: modified phosphate dihydric salt binder 50.0g, nano material dispersion pulp 5.0g, Scale filler is scale
Graphite 18.0g, flake nano material graphene 2.0g, Heatproof anticorrosion pigment zinc oxide 15.0g, anti-settling agent rectorite 2.0g, water
8.0g.Wherein the group of nano material dispersion pulp becomes nano silica 1.0g, 3- aminopropyl triethoxysilane 1.0g, and water is
3.0g。
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: part water and nano silica is taken to stir evenly, and under agitation
40 DEG C are gradually warming up to, is added dropwise and dispersing agent 3- aminopropyl triethoxysilane is added, after being stirred to react 1h, supply surplus moisture,
Nano material dispersion pulp is obtained to the discharging of complete cooled and filtered.
Two, part water and anti-settling agent rectorite, modified phosphate binder, Heatproof anticorrosion pigment oxidation coating preparation: are taken
Zinc is added in stirred tank, and on-line velocity is to stir 10min under 1.0m/s, overground to be ground to fineness≤40 μm, obtains the first mixing
Material；
The water of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
The high temperature resistant graphene anticorrosion coating material for four main tubes of boiler is obtained after uniformly.
Coating property: the coating density (25 DEG C, normal pressure) is 1.55g/cm3, viscosity (25 DEG C, 4# glasss of painting) 60s, solid content
It is 66%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 10 times, coating is intact；550℃
Fused salt (sodium sulphate: potassium chloride) steam 1000h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode
1000h, coating Non Apparent Abnormality.
Embodiment 2:
Raw material proportioning: modified phosphate dihydric salt binder 30.0g, nano material dispersion pulp 5.0g, Scale filler is mica
19.0g, flake nano material graphene 1.0g, Heatproof anticorrosion pigment zinc oxide, trbasic zinc phosphate, polyphosphoric acids aluminium each 5.0g are anti-settling
Agent cellulose 0.5g, water 29.5g.Wherein the group of nano material dispersion pulp becomes nano aluminium oxide 0.8g, nanometer aluminium powder 0.2g,
γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane 1.0g, water 3.0g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: taking part water and nano aluminium oxide to stir evenly, and under agitation by
Step is warming up to 60 DEG C, is added dropwise and dispersing agent γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane is added, and after being stirred to react 2h, mends
Sufficient moisture, after cooling down completely, filtering and discharging obtains nano material dispersion pulp.
Two, part water and anti-settling agent rectorite, cellulose, modified phosphate dihydric salt binder, heat-resisting anti-coating preparation: are taken
Rotten pigment zinc oxide, trbasic zinc phosphate, polyphosphoric acids aluminium are added in stirred tank, stir 20min, mistake under being 1.0m/s in stirring linear velocity
Barreling is milled to fineness≤40 μm, obtains the first mixed material；
The water of mica sheet, nano material dispersion pulp, graphene and surplus is added into the first mixed material, stirring is equal
Filtering and discharging after even, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.50g/cm3, viscosity (25 DEG C, 4# glasss of painting) 50s, solid content
It is 56%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 1 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 9 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 1000h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h,
Coating Non Apparent Abnormality.
Embodiment 3:
Raw material proportioning: modified alkali metal silicate binder 35.0g, nano material dispersion pulp 8.0g, Scale filler is squama
Piece graphite 15.0g and mica sheet 5.0g, flake nano material graphene 5.0g, Heatproof anticorrosion pigment trbasic zinc phosphate, polyphosphoric acids aluminium
Each 5.0g, anti-settling agent rectorite and cellulose each 1.0g, water 20.0g.Wherein the group of nano material dispersion pulp becomes nano oxidized
Titanium 1.6g, γ-(methacryloxypropyl) propyl trimethoxy silicane 1.6g, water 4.8g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: taking part water and nano-titanium oxide to stir evenly, and under agitation by
Step is warming up to 80 DEG C, is added dropwise and dispersing agent-(methacryloxypropyl) propyl trimethoxy silicane is added, and after being stirred to react 1.5h, mends
Sufficient surplus moisture obtains nano material dispersion pulp to the discharging of complete cooled and filtered.
Two, part water and anti-settling agent rectorite, modified alkali silicate, Heatproof anticorrosion pigment oxidation coating preparation: are taken
Zinc is added in stirred tank, stirs 30min under being 1.0m/s in stirring linear velocity, overground to be ground to fineness≤40 μm, obtains first
Mixed material；
The water of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
Filtering and discharging after uniformly, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.48g/cm3, viscosity (25 DEG C, 4# glasss of painting) 55s, solid content
It is 55%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 1 grade；600 DEG C to normal temperature air thermal shock 9 times, coating is intact；550 DEG C to normal-temperature water thermal shock 9 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 900h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h, apply
Layer Non Apparent Abnormality.
Embodiment 4:
Raw material proportioning: modified alkali metal silicate binder 65.0g, nano material dispersion pulp 10.0g, Scale filler is squama
Piece graphite 4.0g, flake nano material graphene 1.0g, Heatproof anticorrosion pigment trbasic zinc phosphate 5.0g, polyphosphoric acids aluminium 5.0g, oxidation
Zinc 5.0g, anti-settling agent rectorite 2.0g, water 3.0g.Wherein the group of nano material dispersion pulp becomes nano titanium powder 1.0g, Nano-Zinc
Powder 1.0g, ethyl orthosilicate 2g, water 6g.
Preparation step is as shown in Figure 1:
One, it the preparation of nano material dispersion pulp: takes part water and nano titanium powder, nano zinc powder to stir evenly, and is stirring
Under the conditions of be gradually warming up to 70 DEG C, be added dropwise and dispersing agent ethyl orthosilicate be added, after being stirred to react 1h, supply moisture, to completely cold
But filtering and discharging obtains nano material dispersion pulp after.
Two, part water and anti-settling agent rectorite, modified alkali metal silicate binder, heat-resistant anticorrosive face coating preparation: are taken
Expect that zinc oxide, trbasic zinc phosphate, polyphosphoric acids aluminium are added in stirred tank, on-line velocity is that 15min is stirred under 2m/s, overground to be ground to carefully
≤ 40 μm of degree, obtains the first mixed material；
The water of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
Filtering and discharging after uniformly, is made the high-temperature resistant anti-corrosive coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.5g/cm3, viscosity (25 DEG C, 4# glasss of painting) 50s, solid content
It is 52%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 9 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 1000h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h,
Coating Non Apparent Abnormality.
Embodiment 5:
Raw material proportioning: polyorganosiloxane resin 40.0g, nano material dispersion pulp 4.0g, Scale filler are mica 20.0g, piece
Shape nano material graphene 5.0g, Heatproof anticorrosion pigment zinc oxide and each 10.0g of polyphosphoric acids aluminium, anti-settling agent bentonite 2.0g,
Butanol 9.0g.Wherein the group of nano material dispersion pulp becomes nano-nickel powder 0.8g, tetrabutyl titanate 0.8g, water 2.4g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: part water and nano-nickel powder is taken to stir evenly, and under agitation gradually
60 DEG C are warming up to, is added dropwise and dispersing agent tetrabutyl titanate is added, after being stirred to react 2h, supply surplus moisture, the mistake after cooling down completely
It filters out material and obtains nano material dispersion pulp.
Two, coating preparation: part water and anti-settling agent bentonite, polyorganosiloxane resin, Heatproof anticorrosion pigment zinc oxide is taken to add
Entering in stirred tank, on-line velocity is to stir 20min under 3.0m/s, it is overground to be ground to fineness≤40 μm, obtain the first mixed material；
The water of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
Filtering and discharging after uniformly, is made the high-temperature resistant anti-corrosive coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.6g/cm3, viscosity (25 DEG C, 4# glasss of painting) 80s, solid content
It is 64%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 1 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 10 times, coating is intact；550℃
Fused salt (sodium sulphate: potassium chloride) steam 900h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h,
Coating Non Apparent Abnormality.
Embodiment 6:
Raw material proportioning: modified polysiloxane resin 55.0g, nano material dispersion pulp 1.0g, Scale filler is crystalline flake graphite
12.0g, flake nano material graphene 3.0g, Heatproof anticorrosion pigment trbasic zinc phosphate 25.0g, anti-settling agent bentonite 3.0g, butanol
1.0g.Wherein the group of nano material dispersion pulp becomes nanometer chromium powder and zirconium-n-butylate each 0.1g, water 0.8g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: part water and nanometer chromium powder is taken to stir evenly, and under agitation gradually
60 DEG C are warming up to, is added dropwise and dispersing agent zirconium-n-butylate is added, after being stirred to react 1h, supply surplus moisture, the mistake after cooling down completely
It filters out material and obtains nano material dispersion pulp.
Two, coating preparation: butanol, bentonite and part polyorganosiloxane resin, the addition of Heatproof anticorrosion pigment trbasic zinc phosphate is taken to stir
It mixes in kettle, on-line velocity is to stir 30min under 5.0m/s, it is overground to be ground to fineness≤40 μm, obtain the first mixed material；
The polyorganosiloxane resin of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added to the first mixing
In material, filtering and discharging, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler after mixing evenly.
Coating property: the coating density (25 DEG C, normal pressure) is 1.3g/cm3, viscosity (25 DEG C, 4# glasss of painting) 75s, solid content
It is 65%.
Film performance: measure the film is 1000 DEG C heat-resisting, 800h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 9 times, coating is intact；550 DEG C to normal-temperature water thermal shock 8 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 800h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h, apply
Layer Non Apparent Abnormality.
Embodiment 7:
Raw material proportioning: modified phosphate dihydric salt binder 30.0g, glass powder 15.0g, nano material dispersion pulp 6.0g, squama
Piece filler is crystalline flake graphite 8.0g, mica 10.0g, flake nano material graphene 2.0g, Heatproof anticorrosion pigment polyphosphoric acids aluminium
5.0g, anti-settling agent cellulose 1.0g, water 23.0g.Wherein the group of nano material dispersion pulp becomes nanometer niobium powder 1.0g, aluminium isopropoxide
1.0g, water 4.0g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: part water and nanometer niobium powder is taken to stir evenly, and under agitation gradually
90 DEG C are warming up to, is added dropwise and isopropyl alcohol dispersant aluminium is added, after being stirred to react 1h, surplus moisture is supplied, to complete cooled and filtered
Discharging obtains nano material dispersion pulp.
Two, coating preparation: taking part water and anti-settling agent cellulose to be added in stirred tank, is 2.0m/s's in stirring linear velocity
Under the conditions of stirring and dissolving, again be added modified phosphate dihydric salt, Heatproof anticorrosion pigment polyphosphoric acids aluminium and glass powder stirring
20min, it is overground to be ground to fineness≤40 μm, obtain the first mixed material；
The water of crystalline flake graphite and mica, nano material dispersion pulp and surplus is added into the first mixed material, is stirred
Filtering and discharging after uniformly, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.4g/cm3, viscosity (25 DEG C, 4# glasss of painting) 65s, solid content
It is 55%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 1 grade；600 DEG C to normal temperature air thermal shock 11 times, coating is intact；550 DEG C to normal-temperature water thermal shock 11 times, coating is intact；550℃
Fused salt (sodium sulphate: potassium chloride) steam 800h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h,
Coating Non Apparent Abnormality.
Embodiment 8:
Raw material proportioning: modified alkali metal silicate binder 55.0g, glass powder 5.0g, nano material dispersion pulp 8.0g, squama
Piece filler is mica 7.0g, flake nano material graphene 3.0g, Heatproof anticorrosion pigment trbasic zinc phosphate, zinc oxide, polyphosphoric acids aluminium
Each 5.0g, anti-settling agent rectorite 4.0g, water 3.0g.Wherein the group of nano material dispersion pulp becomes nano-nickel powder 1.0g, nano aluminum
Powder 0.5g, γ-(methacryloxypropyl) propyl trimethoxy silicane 0.8g, zirconium-n-butylate 0.7g, water 7.0g.
Preparation step is as shown in Figure 1:
One, the preparation of nano material dispersion pulp: part water and nano-nickel powder is taken to stir evenly, and under agitation gradually
50 DEG C are warming up to, is added dropwise and dispersing agent γ-(methacryloxypropyl) propyl trimethoxy silicane, zirconium-n-butylate is added, stirring is anti-
After answering 1h, surplus moisture is supplied, after cooling down completely, filtering and discharging obtains nano material dispersion pulp.
Two, part water and anti-settling rectorite, modified alkali metal silicate binder, Heatproof anticorrosion pigment coating preparation: are taken
Trbasic zinc phosphate, polyphosphoric acids aluminium and zinc oxide are added in stirred tank, and on-line velocity is to stir 30min under 2.0m/s, overground to be ground to
Fineness≤40 μm obtain the first mixed material；
The water of mica, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred evenly
The high temperature resistant graphene anticorrosion coating material for four main tubes of boiler is made in filtering and discharging afterwards.
Coating property: the coating density (25 DEG C, normal pressure) is 1.35g/cm3, viscosity (25 DEG C, 4# glasss of painting) 88s, solid content
It is 58%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 1 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 9 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 900h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h, apply
Layer Non Apparent Abnormality.
Embodiment 9:
Raw material proportioning: polyorganosiloxane resin 30.0g, glass powder 30.0g, nano material dispersion pulp 7.0g, Scale filler are
Crystalline flake graphite 4.0g, flake nano material graphene 1.0g, Heatproof anticorrosion pigment trbasic zinc phosphate and each 5.0g of zinc oxide, anti-settling agent are swollen
Moisten soil 2.0g, butanol 16.0g.Wherein the group of nano material dispersion pulp becomes nanometer chromium powder and each 1.0g of nano zinc powder, dispersing agent
3- aminopropyl triethoxysilane 1.2g, aluminium isopropoxide 0.2g, water 4.6g.
Preparation step is as shown in Figure 1:
One, it the preparation of nano material dispersion pulp: takes part water and nanometer chromium powder, nano zinc powder to stir evenly, and is stirring
Under the conditions of be gradually warming up to 40 DEG C, be added dropwise and dispersing agent 3- aminopropyl triethoxysilane and aluminium isopropoxide be added, be stirred to react 1h
Afterwards, surplus moisture is supplied, obtains nano material dispersion pulp to the discharging of complete cooled and filtered.
Two, part butanol and anti-settling agent bentonite, polyorganosiloxane resin, glass powder, Heatproof anticorrosion pigment coating preparation: are taken
Zinc oxide, trbasic zinc phosphate are added in stirred tank, and on-line velocity is to stir 10min under 1.0m/s, overground to be ground to fineness≤40 μm, obtain
To the first mixed material；
The butanol of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
Filtering and discharging after mixing uniformly, is made the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.45g/cm3, viscosity (25 DEG C, 4# glasss of painting) 45s, solid content
It is 62%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 11 times, coating is intact；550 DEG C to normal-temperature water thermal shock 10 times, coating is intact；550℃
Fused salt (sodium sulphate: potassium chloride) steam 900h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 1000h,
Coating Non Apparent Abnormality.
Below in conjunction with specific comparative example, where further specifically disclosing essence of the invention, but should not be understood as to this
Any restriction of invention enforceable range.
Comparative example 1:
Do not add that nano material dispersion pulp, remaining is identical with embodiment 1, wherein the nano material dispersion pulp removed
Amount is substituted with decentralized medium water.
Raw material proportioning: modified phosphate dihydric salt binder 50.0g, Scale filler are crystalline flake graphite 18.0g, flake nano material
Expect graphene 2.0g, Heatproof anticorrosion pigment zinc oxide 15.0g, anti-settling agent rectorite 2.0g, water 13.0g.
Preparation step: part water and anti-settling agent rectorite, modified phosphate binder, Heatproof anticorrosion pigment zinc oxide is taken to add
Entering in stirred tank, on-line velocity is to stir 10min under 1.0m/s, it is overground to be ground to fineness≤40 μm, obtain the first mixed material；
The water of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is stirred
Filtering and discharging after uniformly, is made the high-temperature resistant anti-corrosive coating material for four main tubes of boiler.
Coating property: the coating density (25 DEG C, normal pressure) is 1.55g/cm3, viscosity (25 DEG C, 4# glasss of painting) 58s, solid content
It is 65%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 10 times, coating is intact；550 DEG C to normal-temperature water thermal shock 10 times, coating is intact；550℃
Fused salt (sodium sulphate: potassium chloride) steam 500h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 600h,
Coating Non Apparent Abnormality.
Comparative example 2:
Do not add that Scale filler, remaining is identical with embodiment 4, wherein the amount decentralized medium of the Scale filler removed
Water substitution.
Raw material proportioning: modified alkali metal silicate binder 65.0g, nano material dispersion pulp 10.0g, flake nano material
Graphene 1.0g, Heatproof anticorrosion pigment trbasic zinc phosphate 5.0g, polyphosphoric acids aluminium 5.0g, zinc oxide 5.0g, anti-settling agent rectorite 2.0g,
Water 7.0g.Wherein the group of nano material dispersion pulp becomes nano titanium powder 1.0g, nano zinc powder 1.0g, ethyl orthosilicate 2g, and water is
6g。
Preparation step:
One, it the preparation of nano material dispersion pulp: takes part water and nano titanium powder, nano zinc powder to stir evenly, and is stirring
Under the conditions of be gradually warming up to 70 DEG C, be added dropwise and dispersing agent ethyl orthosilicate be added, after being stirred to react 1h, supply moisture, to completely cold
But filtering and discharging obtains nano material dispersion pulp after.
Two, part water and anti-settling agent rectorite, modified alkali metal silicate binder, heat-resistant anticorrosive face coating preparation: are taken
Expect that zinc oxide, trbasic zinc phosphate, polyphosphoric acids aluminium are added in stirred tank, on-line velocity is that 15min is stirred under 2m/s, overground to be ground to carefully
≤ 40 μm of degree, obtains the first mixed material；
The water of nano material dispersion pulp, graphene and surplus is added into the first mixed material, after mixing evenly mistake
Material is filtered out, the high temperature resistant graphene anticorrosion coating material for four main tubes of boiler is made.
Coating property: the coating density (25 DEG C, normal pressure) is 1.55g/cm3, viscosity (25 DEG C, 4# glasss of painting) 30s, solid content
It is 47%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 8 times, coating is intact；550 DEG C to normal-temperature water thermal shock 7 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 500h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 600h, apply
Layer Non Apparent Abnormality.
Comparative example 3:
Do not add that Heatproof anticorrosion pigment, remaining is identical with embodiment 9, wherein the amount for the Heatproof anticorrosion pigment removed is used
Decentralized medium butanol substitution.
Raw material proportioning: polyorganosiloxane resin 30.0g, glass powder 30.0g, nano material dispersion pulp 7.0g, Scale filler are
Crystalline flake graphite 4.0g, flake nano material graphene 1.0g, anti-settling agent bentonite 2.0g, butanol 26.0g.Wherein nano material point
The group for dissipating slurry becomes nanometer chromium powder and each 1.0g of nano zinc powder, dispersing agent 3- aminopropyl triethoxysilane 1.2g, aluminium isopropoxide
0.2g, water 4.6g.
Preparation step:
One, it the preparation of nano material dispersion pulp: takes part water and nanometer chromium powder, nano zinc powder to stir evenly, and is stirring
Under the conditions of be gradually warming up to 40 DEG C, be added dropwise and dispersing agent 3- aminopropyl triethoxysilane and aluminium isopropoxide be added, be stirred to react 1h
Afterwards, surplus moisture is supplied, obtains nano material dispersion pulp to the discharging of complete cooled and filtered.
Two, coating preparation: taking part butanol and anti-settling agent bentonite, polyorganosiloxane resin, glass powder to be added in stirred tank,
On-line velocity is to stir 10min under 1.0m/s, overground to be ground to fineness≤40 μm, obtains the first mixed material；
The butanol of crystalline flake graphite, nano material dispersion pulp, graphene and surplus is added into the first mixed material, is made
With the high-pressure homogeneous dispersion machine of controllable temperature with 25 DEG C of temperature, pressure 200MPa makes coating perfectly homogenousization, until after granularity is less than 25 μm
The high temperature resistant graphene anticorrosion coating material for four main tubes of boiler is made in filtering and discharging.
Coating property: the coating density (25 DEG C, normal pressure) is 1.35g/cm3, viscosity (25 DEG C, 4# glasss of painting) 35s, solid content
It is 52%.
Film performance: measure the film is 1000 DEG C heat-resisting, 1000h without cracking, the abnormal phenomenon such as peel off；Adhesive force (draws lattice
Method) 0 grade；600 DEG C to normal temperature air thermal shock 6 times, coating is intact；550 DEG C to normal-temperature water thermal shock 5 times, coating is intact；550 DEG C molten
Salt (sodium sulphate: potassium chloride) steam 300h, coating are intact.550 DEG C of reducing atmosphere (CO:SO2: H2S:HCl) corrode 500h, apply
Layer Non Apparent Abnormality.
Comparative example 4:
Raw material proportioning: organosilicon epoxy resin polymer W800 (Wuhan Inst of Modern Industry Technology) 55%, salt fog resistance
Auxiliary agent SN (Shanghai Ou Chen material science and technology Development Co., Ltd) 1%, copper ferrochrome black 953 (upper sea God's promise trade Co., Ltd) 6%,
(lattice sharp mining industry in Chuzhou has by nano zine oxide NAOAZO (Zhuzhou Zhongle Chemical Industry Co., Ltd.) 2%, flake mica powder GA-1
Limit responsible company) 6%, aluminium triphosphate (Qingzhou City hundred million surpasses Chemical Co., Ltd.) 7%, levelling agent BYK306 0.1%, defoaming
Agent BYK066N (German Bi Ke chemistry) 0.2%, dispersant B YK104S 0.2%, talcum powder (Wuxi Red Star mountain flour factory) 4%, two
Toluene (the wooden Chemical Co., Ltd. in Jiangsu three) 18.5%.
Paint film property:
1, high temperature resistance: 500 DEG C × 100h paint film is not cracked, is not fallen off, only light discolouration；
2, adhesive force: 1 grade；
3, flexibility: 1mm；
4, impact: 50cm；
5, salt fog resistance: resisting salt fog corrosion 48h paint film is not corroded, is not fallen off after heat-resisting 500 DEG C × 10h, only light discolouration.
Pass through the comparison of the above comparative example and embodiment, it can be clearly seen that, since consumption of binder and type are unchanged,
Therefore the heat resistance of coating and adhesive force are without significant change；Under when not adding nano material, the Corrosion Protection of coating is obvious
Drop, this is because the introducing of nano material promotes the compactness of coating significantly, the promotion of coating compactness means coating
Promotion to the screening ability of corrosive medium, the i.e. promotion of the antiseptic property of coating；When not adding scale material, the heat of coating
Shake and antiseptic property are decreased obviously, this is because flakey material includes one, good shielding properties, two, the mistake of stratified material
Cropping sets the thermal matching that can effectively promote coating material and metal substrate, makes with the anti-corrosion of the coating when not adding scale material
It is decreased obviously with thermal shock；When not adding Heatproof anticorrosion pigment, the thermal shock of coating and anti-corrosion can be also decreased obviously, and reason has two:
One, Heatproof anticorrosion pigment in the coating when itself have good antiseptic property, so antiseptic property is decreased obviously when not adding,
Two, Heatproof anticorrosion pigment itself has different particle diameter distributions, is arranged in pairs or groups by the gradation of different-grain diameter, also can effectively promote painting
Thermal matching between layer and metal substrate.In short, nano material, scale material and Heatproof anticorrosion pigment all have in a certain respect
Advantage performance can just coating performance be made to be optimal by synergistic effect between them and perfect collocation.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in protection model of the invention within the spirit and principle of invention
Within enclosing.
Claims (10)
1. a kind of graphene coating material protected in advance for four main tubes of boiler high temperature corrosion, which is characterized in that by mass percentage
Meter, including component:
Wherein, the nano material dispersion pulp is to be carried out at cladding by the organic compound containing functional group to nano-powder
The composition formed after reason.
2. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the high temperature resistant adhesive is modified phosphate dihydric salt, modified alkali silicate, by sol-gel method preparation
At least one of polyorganosiloxane resin, glass powder.
3. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the nano material dispersion pulp includes component by mass percentage:
Nano material 0.1~20%
Dispersing agent 0.1~20%
Water 60~99.8%；
Wherein, the nano material, particle size are 10nm~500nm.
4. the graphene coating material according to claim 3 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the nano material includes nano silica, nano aluminium oxide, nano-titanium dioxide, nano titanium powder, nano-nickel powder, receives
At least one of rice chromium powder, nanometer niobium powder, nanometer aluminium powder, nano zinc powder, it is mixed by any mass percent when to be a variety of
It closes；
The dispersing agent is the organic compound containing functional group, including 3- aminopropyl triethoxysilane, γ-(2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, ethyl orthosilicate, the positive fourth of metatitanic acid
At least one of ester, zirconium-n-butylate, aluminium isopropoxide are mixed when to be a variety of by any mass percent.
5. the graphene coating material according to claim 3 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the preparation process of the nano material dispersion pulp are as follows: take part water and nano material to stir evenly, and under agitation
40 DEG C to 90 DEG C are gradually warming up to, is added dropwise and dispersing agent is added, be stirred to react 1 to 2h, the water that surplus is added stirs evenly, cooling
Filtering and discharging obtains nano material dispersion pulp afterwards.
6. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the Scale filler is at least one of crystalline flake graphite, flake mica, mixed by any mass percent when for two kinds
It closes.
7. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the flake nano material is graphene, and piece diameter is not more than 10 μm, and thickness is not more than 0.01 μm.
8. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the Heatproof anticorrosion pigment is at least one of trbasic zinc phosphate, polyphosphoric acids aluminium, zinc oxide, when to be a variety of, by any matter
Measure percentage mixing.
9. the graphene coating material according to claim 1 protected in advance for four main tubes of boiler high temperature corrosion, feature exist
In the anti-settling agent is at least one of rectorite, bentonite, cellulose, mixed by any mass percent when to be a variety of
It closes.
10. a kind of graphene coating material as described in any one of claims 1 to 9 protected in advance for four main tubes of boiler high temperature corrosion
Preparation method for material, which is characterized in that the preparation method includes the following steps:
High temperature resistant adhesive, Heatproof anticorrosion pigment and anti-settling agent are proportionally added into decentralized medium, with 1~5m/s of linear velocity
10~30min is stirred, fineness≤40 μm is ground to after mixing evenly, obtains the first mixed material；
Scale filler, nano material dispersion pulp and/or flake nano material are proportionally added into the first mixed material, stirred
Filtering and discharging after uniformly, is made the graphene coating material protected in advance for four main tubes of boiler high temperature corrosion.
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| CN111849226A (en) * | 2020-06-19 | 2020-10-30 | 马鞍山致青工业设计有限公司 | Temperature-change-resistant corrosion-resistant coating for inner wall of heating tube and preparation method thereof |
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| CN114644843A (en) * | 2020-12-18 | 2022-06-21 | 深圳优易材料科技有限公司 | Anticorrosive and anti-sticking coating for grate segment of garbage incinerator and preparation method and application thereof |
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| CN114479530A (en) * | 2022-03-07 | 2022-05-13 | 邱质彬 | High-compactness long-acting anti-corrosion coating suitable for heating surface of biomass boiler |
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