CN106905723A - The coating of anti-coking, the product for having anti-coking coating and the method for preventing product coking - Google Patents
The coating of anti-coking, the product for having anti-coking coating and the method for preventing product coking Download PDFInfo
- Publication number
- CN106905723A CN106905723A CN201510977017.7A CN201510977017A CN106905723A CN 106905723 A CN106905723 A CN 106905723A CN 201510977017 A CN201510977017 A CN 201510977017A CN 106905723 A CN106905723 A CN 106905723A
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- China
- Prior art keywords
- coking
- coating
- product
- inorganic binder
- slurry
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 106
- 239000011248 coating agent Substances 0.000 title claims abstract description 96
- 238000004939 coking Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
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- 239000002002 slurry Substances 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 15
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- 239000002904 solvent Substances 0.000 claims description 8
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- 239000001301 oxygen Substances 0.000 claims description 7
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- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of anti-coking coating includes anti-coking catalysis material and inorganic binder, wherein, the inorganic binder includes phosphate, silicate, or combinations thereof.A kind of product for being coated with the anti-coking coating and a kind of product is protected by the anti-coking coating in case it is due to the method exposed to fuel combustion environment and coking.
Description
Technical field
This invention relates generally to a kind of coating of anti-coking, the product with anti-coking coating and prevent
The method of product coking.
Background technology
In liquid fuel or binary fuel combustion system, coking is a kind of common phenomenon.For example,
During INVENTIONLiquid-fueled combustion, coke may be deposited in the nozzle surface of gas turbine or engine.
In nozzle overheat and the fuel holdup time it is long due to cause fuel occur chemical breakdown, may
There is inside in the way of carbonaceous material deposition (namely coke laydown) on nozzle interior fuel channel
Coking.Cause the deposition of carbonaceous material due to there is distillation of fuel and/or liquid phase reactor in outer surface, in spray
The hot outer surface of mouth is likely to therefore outside coking or carbonization.Due to the accumulation of coke, nozzle
Surface can gradually form one layer of coking layer, and this may reduce the efficiency of combustion system, even result in potential
Safety problem.And, the accumulation of coke can have adverse effect on to the physical property of nozzle, make to hold
The mechanical performances such as long intensity, thermal fatigue resistance, ductility are degenerated.Accordingly, it would be desirable to periodically be devoked.
But decoking may interrupt production process, operating cost is improved.
There are various methods to be considered for eliminating the unit such as nozzle due to coke build-up gas turbine or engine
The harm brought on part.These methods include：Start with from metallurgical angle, nozzle metallic matrix material of upgrading
Material；Structure optimization is carried out to diplopore nozzle, to overcome the problem of the secondary fuel channel interior coking of nozzle；
Selective pretreatment is carried out to inner nozzle surface；Use inactive surfaces coating；Catalytic gasification coke is generated
CO/CO2And hydrogen.
Although above-mentioned certain methods are commonly used in the industry, people still expect to have a kind of new
Method, is avoided that or makes up the deficiency of preceding method, and can successfully reduce or eliminate coking.
The content of the invention
On the one hand, a kind of anti-coking coating includes anti-coking catalysis material and inorganic binder.Wherein, institute
Stating inorganic binder includes phosphate, silicate, or combinations thereof.
On the other hand, a kind of product includes metallic matrix and the anti-coking coating on the metallic matrix.
The anti-coking coating includes anti-coking catalysis material and inorganic binder.Wherein described inorganic binder includes
Phosphate, silicate or combinations thereof.
On the other hand, it is a kind of to protect the product in case it is due to exposed to the side of fuel combustion environment and coking
Method, it includes:The coating slurry on the product；And the coating is calcined at the temperature below 900 DEG C
There is the product of slurry.The slurry includes anti-coking catalysis material and inorganic binder.Wherein this is inorganic viscous
Knot agent includes phosphate, silicate or combinations thereof.
Brief description of the drawings
When reading described in detail below referring to the drawings, these and other features of the invention, aspect and excellent
Point will become better understood, and in the accompanying drawings, identical element numbers are used to represent identical in whole accompanying drawings
Part, wherein：
Figure 1A shows the La obtained in example 12NiO4The microstructure of base coating.
Figure 1B is shown in each circulation of crude oil oven test respectively in the La of example 12NiO4Base is applied
The contrast of the cinder weight not claimed on cated bare board on layer and at one.
Fig. 2A shows the La obtained in example 21.3K0.3Ba0.4NiO4The microstructure of base coating.
Fig. 2 B are shown in each circulation of crude oil oven test respectively in example 2
La1.3K0.3Ba0.4NiO4The cinder weight that does not claim on cated bare board on base coating and at one
Contrast.
Fig. 3 A show the Sr obtained in example 31.8K0.2MnO4The microstructure of base coating.
Fig. 3 B are shown in each circulation of crude oil oven test respectively in the Sr of example 31.8K0.2MnO4
The contrast of the cinder weight not claimed on cated bare board on base coating and at one.
Fig. 4 A show the SrCO obtained in example 43The microstructure of base coating.
Fig. 4 B are shown in each circulation of crude oil oven test respectively in the SrCO of example 43Base is applied
The contrast of the cinder weight not claimed on cated bare board on layer and at one.
Fig. 5 A show the SrCO obtained in example 53The microstructure of-NiO base coatings.
Fig. 5 B are shown in each circulation of crude oil oven test respectively in the SrCO of example 53-NiO
On base coating and in the contrast for the cinder weight not claimed on cated bare board of.
Fig. 6 A show the Aln (PO obtained in example 6x) coating microstructure.
Fig. 6 B are shown in each circulation of crude oil oven test respectively in the Aln (PO of example 6x) apply
The contrast of the cinder weight not claimed on cated bare board on layer and at one.
Specific embodiment
Unless otherwise defined, the technical term for using in the present specification and claims or section are academic
Language should be the ordinary meaning that the personage with general technical ability is understood in the technical field of the invention.This
" first " or " second " and similar word used in specification and claims are not offered as
Any order, quantity or importance, and be used only to distinguish different parts." one " or
The similar word such as " one " is not offered as quantity limitation, but expression has at least one.It is used herein
The language of approximation can be used for quantitative expression, show that number can be allowed in the case where basic function is not changed
Amount has certain variation.Therefore, the numerical value corrected with the language such as " about ", " left and right " is not limited to the standard
Exact figures value is in itself.Additionally, in the statement of " the about first numerical value to second value ", " about " is while amendment the
One numerical value and second value two values.In some cases, approximating language may be with measuring instrument
Precision is relevant.Numerical value mentioned in the present invention includes the increased institute of one unit of a unit from low to high
There is numerical value, it is assumed herein that being spaced Unit at least two between any lower value and high value.
The all of numerical value between minimum to peak enumerated herein, refers to when minimum and most
Differed when more than two units between high level, obtained by increment of a unit between minimum and peak
All numerical value.Such as, the quantity and the numerical value of process of the component being similar to as temperature, air pressure, time etc.
Deng when we say 1 to 90, reference is such as 15 to 85,22 to 68,43 to 51,30 to arrive
The similar enumerated value of 32 grades.When numerical value is less than 1, a unit can be 0.0001,0.001,0.01
Or 0.1.Merely just illustrated as particular examples.The numeral for including herein refers to use similar
The all possible combinations of values between a minimum value and a maximum value that method is obtained.
Embodiments of the invention are related to reduce or eliminate in fuel, and particularly liquid fuel and binary fuel fire
Used in burning environment, for example, used in the INVENTIONLiquid-fueled combustion environment of gas turbine or engine
The method of the coke build-up on metallic article.The method is related to coat anti-coking on the metallic matrix of product
Catalysis material is formed with the catalyst coatings of good anticoking capability.The anti-coking catalysis material can drop
The firing point (i.e. carbonaceous material starts the minimum temperature of burning) of the carbonaceous materials such as low-carbon (LC), for example, from about
600 DEG C fall below 400 DEG C or less than 300 DEG C, and/or improve the burning velocity of carbonaceous material.Cause
This, in the presence of the catalysis material, coke or petroleum residue can at a lower temperature and/or
Burnt under burning velocity higher, even if thus the fuel combustion betides relatively low temperature,
Still coke build-up can effectively be prevented.
The anti-coking catalysis material can be that STRENGTH ON COKE burning has catalysis activity and can reduce the carbonaceous material such as carbon
The firing point of material and/or any suitable material of raising carbonaceous material burning velocity.Some anti-cokings are catalyzed
The example of material includes but are not limited to Perovskite Phase related compounds, spinelle, carbonate, noble metal.
" Perovskite Phase related compounds " as herein described refer to that simplified expression is AaBbOoCompound,
Wherein, A is A material for occupying A (oxygen tetrahedral interstice), and B is to occupy B (oxygen octahedral
Body space) B material, O is oxygen, and what a, b and o were represented makes the compound have single-phase
The stoichiometric number of correspondence each element." spinelle " as herein described refers to that simplified expression is XY2O4
(X2+Y3+ 2O2- 4) compound.So simplify the compound of formula.Although in typical spinelle knot
In structure, X and Y is respectively+divalent and+trivalent, but in fact, monovalence, divalence, trivalent or tetravalence sun
Ion, such as potassium, magnesium, aluminium, iron, zinc, manganese, chromium, the combination of silicon are also possible.
In certain embodiments, the anti-coking catalysis material includes that simplified expression is An+1BnO3n+1's
Perovskite Phase related compounds, wherein, A is A material for occupying A (oxygen tetrahedral interstice), B
To occupy B (oxygen octahedra gap) B material, O is oxygen, n >=1.The perovskite related compounds
Thing may include perovskite or perovskite-like oxide, such as be referred to as the layer of Ruddlesden-Popper phases
Shape perovskite structure.Especially, when n tends to infinity, acquisition is perovskite, and it simplifies expression
Formula is ABO3.In certain embodiments, A material or B material may include at least one selected from alkali
Element in metal, alkaline-earth metal, rare earth metal and transition metal.In some specific embodiments,
A material includes at least one element selected from alkali metal, alkaline-earth metal and rare earth metal.B material
Material includes at least one transition metal.
" alkali metal " as herein described refers to that the periodic table of chemical element (with applied chemistry combine by international theory
Meeting, IUPAC) in the first main group element, including lithium (Li), sodium (Na), potassium (K), rubidium (Rb),
Caesium (Cs) and francium (Fr)." alkaline-earth metal " as herein described refers to the second master in the periodic table of chemical element
The element of race, including beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra).
" rare earth metal " as herein described refers to the set of the 17 elements composition in the periodic table of chemical element,
Including scandium (Sc), yttrium (Y), 15 group of the lanthanides and any combination of them.Wherein, described 15
Lanthanide series includes lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm, europium
(Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium
And lutetium (Lu) (Yb)." transition metal " as herein described refers in the periodic table of chemical element three and arrives
The element of 12 main groups, including scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron
(Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb),
Molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver-colored (Ag), cadmium (Cd), hafnium
(Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), golden (Au),
Mercury (Hg).
In certain embodiments, the expression formula An+1BnO3n+1In A include Na, K, Ca, Sr,
Ba, La or combinations thereof.In some specific embodiments, the expression formula An+1BnO3n+1In
A include La, alternatively also include dopant, the dopant include Na, K, Ca, Sr, Ba or it
Combination.In certain embodiments, the expression formula An+1BnO3n+1In B include Mn, Co,
Ni or combinations thereof.In some specific embodiments, the expression formula An+1BnO3n+1In B bags
Include Ni.The example of some suitable Perovskite Phase related compounds includes LaNiO3、La0.9Sr0.1NiO3、
La2NiO4、La1.9K0.1NiO4、La1.9Na0.1NiO4、LaSrNiO4、Sr2MnO4、Sr1.8K0.2MnO4With
La1.3K0.3Ba0.4NiO4。
Because coating is generally formed in the fusing point close to the catalysis material, therefore for maximum tolerance temperature
For degree is less than the metallic matrix of the catalysis material fusing point, the catalysis material is formed on its surface
Coating is extremely challenging.Catalysis material can be helped to be combined together shape using a kind of inorganic binder
Into coating.In certain embodiments, the coating further includes a kind of inorganic binder, and it can be low
The coating of the catalysis material is formed on metallic matrix at a temperature of the catalysis material fusing point.Have
The inorganic binder, catalysis material can form coating at a lower temperature, such as at 600 DEG C or so
In on metallic matrix.A kind of suitable inorganic binder is found, it can be used for forming firm catalysis
Coating can make the anticoking capability of catalyst keep good again, and this is challenging.May need to consider
Chemical compatibility between binding agent and catalysis material and catalysis material and matrix between.Furthermore, it is possible to also
The sintering temperature of binding agent species and concentration and coating need to be designed, to avoid to catalyst coatings
Catalysis activity be negatively affected.
In certain embodiments, the inorganic binder includes phosphate, silicate or combinations thereof.
In some specific embodiments, the inorganic binder includes phosphate." phosphate " as herein described
Refer to phosphate radical anion POx, such as PO4 3-、HPO4 2-、H2PO4 -Inorganic compound." silicic acid
Salt " refers to silicate anion SiOx, such as SiO3 2-And SiO4 4-Inorganic compound.At some
In specific embodiment, the inorganic binder includes aluminium dihydrogen phosphate (Al (H2PO4)3), phosphoric acid hydrogen aluminium
(Al2(HPO4)3), aluminum phosphate (Al·n(POx)), potassium silicate (K-Si-O, such as K2SiO3Or K4SiO4)、
Sodium metasilicate (Na-Si-O, such as Na2SiO3Or Na4SiO4) or combinations thereof.Have described inorganic
Binding agent, can at relatively low temperature obtain all good anti-coking coating of uniformity and mechanical performance.
Additionally, the inorganic binder in coating will not accelerate the deposition of coke, so that coating can guarantee that well
Catalysis activity.
In certain embodiments, the inorganic binder relative to the mass percent of the coating about 1%
To about 90% scope, the catalysis material relative to the coating mass percent about 10% to about
99% scope.
One kind is further related in embodiments of the invention to be protected by forming the anti-coking coating on product
The product is protected in case the method for its coking by exposure to fuel combustion environment.In the method, can use
The catalysis material and inorganic binder prepare slurry, then the slurry are passed through into a kind of suitable coating
Technique or method, such as water-laid film (wet-chemical deposition) technique, is coated on product,
Such as it is coated on being exposed on the surface of INVENTIONLiquid-fueled combustion environment for product.Slurry can be coated with by described
Product be dried, to obtain the cated product of covering.The cated product of covering can be entered
Row roasting is sintered.Anti-coking coating can be thus formed on the matrix of product.In certain embodiments,
The roasting or sintering at relatively low temperature, are such as carried out below 900 DEG C.It is specific at some
In embodiment, the roasting or 300 DEG C to 900 DEG C of temperature range is sintered in, or further,
Carried out in 300 DEG C to 600 DEG C temperature ranges.
" slurry " as herein described refers to the fluid mixture of solid (typically solid powder) and liquid.
The property of slurry can be similar with sticky liquid, can flow under gravity, be not very sticky
In the case of also available pump extract." water-laid film (wet-chemical deposition) " refers to based on liquid
The coating process of operation, is related to apply on matrix the precursor layer of liquid, is then made by subsequent treatment
The precursor layer of the liquid is transformed into desired coating.The example of some water-laid film techniques includes that dipping is applied
Apply method (dip coating methods), whirl coating (spin coating methods), spraying process (spray
Coating methods), mould coating process (die coating methods), silk screen print method (screen
printing methods)。
The slurry can also further include a kind of solvent.The solvent may include water, alcohols or they
Combination.The example of some suitable alcohols includes methyl alcohol, ethanol and n-butanol.In certain embodiments,
The inorganic binder includes K2SiO3Or Na2SiO3, the solvent include water.In certain embodiments,
The inorganic binder includes phosphate, such as Aln (POx), the solvent includes alcohols.In some implementations
In example, the weight/mass percentage composition of the anti-coking catalysis material in the slurry is about 30% to about 60%
Scope, the model of the weight/mass percentage composition of the inorganic binder in the slurry about 2% to about 15%
Enclose.The slurry can further include the dispersant for improving solid particle decentralization in the slurry.Institute
Stating slurry can also further include organic binder bond, for example, polyvinyl butyral (PVB).In subsequent shape
During coating, the organic matter in slurry and/or described has for example described solvent, the dispersant
Machine binding agent, may be burned out, and be specifically dependent upon to form what the slurry during coating was reached
Temperature.
Embodiments of the invention further relate to a kind of product for being coated with foregoing anti-coking coating.Aforementioned articles can
Including metallic matrix and the foregoing anti-coking coating being coated on the metallic matrix.The metal
Matrix may be made up of any suitable metal or alloy, include but are not limited to ferrous alloy, cobalt-based and close
Gold, nickel-base alloy or their combination.The anti-coking coating can have acquisition anticoking capability usual
Required suitable thickness.In certain embodiments, the thickness of the anti-coking coating is about 1-200 microns.
The anti-coking coating can be formed by foregoing process.The product can any have one
Exposed to the component on liquid fuel or the surface of binary fuel burning situation, and the anti-coking coating
At least it is coated in the surface for being exposed to liquid fuel or binary fuel burning situation.In some embodiments
In, the product is the nozzle for gas turbine or engine, and the nozzle has at least one to be exposed to
Surface in INVENTIONLiquid-fueled combustion environment.
Embodiments of the invention can be illustrated by referring to some non-limiting examples.Following example meanings
Figure is to elaborate on how to carry out the material and method described in claim to those skilled in the art
Assessment, its should not be taken as any angle for limitation of the invention.
Example
In this example, prepare and test the anti-scorch coating of heterogeneity.Unless otherwise mentioned, institute
Some materials or component can be from the market general chemical suppliers buy.
Al·n(POx) preparation：By 88 grams of ANN aluminium nitrate nonahydrate (H18AlN3O18) use ultrasonication
Mode be dissolved in 79 grams of ethanol, obtain H18AlN3O18Ethanol solution.By 33 grams of phosphorus pentoxide
It is dissolved in 105 grams of ethanol with the mode of ultrasonication, obtains the ethanol solution of phosphorus pentoxide.Will
Two kinds of solution are mixed to get mixed liquor, then by about 5 hours of mixed-liquor return, are subsequently cooled to room temperature,
Obtain Aln (POx) ethanol solution.
The preparation of coating：With the formula prepares coating slurry in table 1 below.It is by 0.1 gram in example 1
La2NiO4, 0.1 gram of sodium metasilicate (522-T, purchased from A Muke (Aremco) Products Co., Ltd, knob
About) and 1 gram of water mixing prepares slurry.It is by 0.5 gram of La in example 21.3K0.3Ba0.4NiO4、
Aln (the PO prepared described in 0.15 gramx) ethanol solution, 0.05 gram of n-butanol and 0.38 gram of second
Alcohol mixes slurry is obtained.It is by 1.0 grams of Sr in example 31.8K0.2MnO4, 0.3 gram of preparation
Good Aln (POx) ethanol solution, 1.0 grams of ethanol, 0.1 gram of polyvinyl butyral resin containing 8wt%
(PVB) ethanol solution (wherein PVB as organic binder bond, ethanol as solvent a part) and
0.2 gram of Disperbyk-110 dispersants (being purchased from BYK Additives＆Instruments companies) are mixed
Close to prepare slurry.It is by 2.0 grams of SrCO in example 43, the Aln (PO prepared described in 0.6 gramx)
Ethanol solution, 0.2 gram of ethanol solution and 0.4 gram of Disperbyk-110 containing 8wt%PVB
Dispersant prepares slurry.In example 5, by 0.44 gram of SrCO3, 0.16 gram of NiO, 0.2 gram
Aln (the PO for preparingx) ethanol solution, 0.6 gram of ethanol, 0.06 gram of second containing 8wt%PVB
Alcoholic solution and 0.1 gram of Disperbyk-110 dispersant are obtained slurry.It is straight in example 6
Meet the Aln (PO prepared described inx) ethanol solution as slurry, and without anti-coking catalyst.
Every part of slurry for preparing is coated on metallic plate respectively, is made coating.In example 1 is spray
The method of painting.Example 2 and 3 be dip coating method, lifting speed be 100mm/min.Each
The metallic plate of coating slurry is placed in air drying, obtains the metallic plate of band coating.Then at about 80 DEG C
Lower drying about 60 minutes, then dries about 60 minutes at about 260 DEG C again.Dried metallic plate exists
It is calcined in air about 2 hours, sintering temperature is about 550 DEG C, and programming rate is about 2 DEG C/min.With so
Method, can obtain La on the metallic plate of example 12NiO4Base coating；Be can obtain on the metallic plate of example 2
La1.3K0.3Ba0.4NiO4Base coating；Sr is can obtain on the metallic plate of example 31.8K0.2MnO4Base coating；Example 4
Metallic plate on can obtain SrCO3Base coating；SrCO is can obtain on the metallic plate of example 53- NiO base coatings；
Aln (PO are can obtain on the metallic plate of example 6x) coating (without catalyst).
Table one
Microstructure and the adhesiveness analysis of coating：Obtained in observing example 1 to 6 with SEM
Coating microstructure.La2NiO4The microstructure of base coating as shown in Figure 1A, from Figure 1A
As can be seen that La2NiO4Base coating is fine and close and flawless.La1.3K0.3Ba0.4NiO4Base coating is as schemed
Shown in 2A, as can be seen that La from Fig. 2A1.3K0.3Ba0.4NiO4Base coating has some crackles.
Sr1.8K0.2MnO4The microstructure of base coating is as shown in Figure 3A.Be can be seen that from Fig. 3 A
Sr1.8K0.2MnO4Base coating also has some crackles.SrCO3The microstructure of base coating is as shown in Figure 4 A.
As can be seen that SrCO from Fig. 4 A3Base coating is fine and close and flawless.SrCO3- NiO base coatings
Microstructure is as shown in Figure 5A.As can be seen from Figure 5A, SrCO3- NiO base coatings be also it is fine and close and
Flawless.Al·n(POx) coating microstructure as shown in Figure 6A, as can be seen from Figure 6A,
Al·n(POx) coating has crackle.Additionally, the adhesive force of each coating is all entered with survey adhesion standard adhesive tape method
Measurement (ASTM D3359-B) is gone.Result finds that six kinds of coatings all have 4-5B grades of good adhesion
Power.
Crude oil roasting test：Test is calcined with crude oil to simulate the combustion process of liquid fuel.In the test
In, respectively toward in exposed heat seal golden plate (not band coating) and being coated with the heat seal golden plate (sample of tested coating
This 1,2,3,4,5 or 6) on spray crude oil, the alloy sheets for being coated with crude oil are placed on box
It is calcined at a temperature of 330 DEG C to 350 DEG C in stove, the coking in the alloy sheets in the process can fire
Burn.After roasting, the cinder to being coated with the alloy sheets of tested coating is weighed, and not coated piece of
The cinder weight claimed in alloy sheets is compared, to assess the anticoking capability of tested coating.If band
Weight of the weight of the cinder claimed in the alloy sheets of coating less than the cinder claimed in not coated piece of alloy sheets
Amount, then the coating is considered as possessing anticoking capability.The weight of the cinder claimed in alloy sheets is smaller, then
The anticoking capability of coating is better.Wherein, the spraying and roasting can be repeated several times and carry out, if will
Once the process of complete spraying and roasting is considered as a circulation, and the crude oil roasting test may include many
Individual circulation.
Evaluating result：Figure 1B shows what is obtained in example 1 respectively in each circulation of crude oil oven test
La2NiO4On base coating and in the contrast for the cinder weight not claimed on cated bare board.From Figure 1B
It can be seen that the former cinder is significantly less weight than the latter, this is indicated that, La2NiO4Base coating has good
Anticoking capability.
Fig. 2 B show what is obtained in example 2 respectively in each circulation of crude oil oven test
La1.3K0.3Ba0.4NiO4On base coating and in the contrast for the cinder weight not claimed on cated bare board.
The former cinder is significantly less weight than the latter as can be seen from Figure 2B, and this is indicated that, La1.3K0.3Ba0.4NiO4
Base coating has good anticoking capability.
Fig. 3 B show what is obtained in example 3 respectively in each circulation of crude oil oven test
Sr1.8K0.2MnO4On base coating and in the contrast for the cinder weight not claimed on cated bare board.From
Fig. 3 B can be seen that the former cinder is significantly less weight than the latter, and this is indicated that, Sr1.8K0.2MnO4Base is applied
Layer has good anticoking capability.
Fig. 4 B show the SrCO obtained in example 4 respectively in each circulation of crude oil oven test3Base is applied
On layer and in the contrast for the cinder weight not claimed on cated bare board.Before as can be seen from Figure 4B
The cinder of person is significantly less weight than the latter, and this is indicated that, SrCO3Base coating has good anticoking capability.
Fig. 5 B show the SrCO obtained in example 5 respectively in each circulation of crude oil oven test3-NiO
On mixture base coating and in the contrast for the cinder weight not claimed on cated bare board.From Fig. 5 B
It can be seen that the former cinder is significantly less weight than the latter, this is indicated that, SrCO3- NiO mixture base coatings
With good anticoking capability.
Fig. 6 B show the Aln (PO obtained in example 6 respectively in each circulation of crude oil oven testx) apply
On layer and in the contrast for the cinder weight not claimed on cated bare board.Before as can be seen from Figure 6B
The cinder weight of person is much larger than the latter, and this shows individually to use Aln (POx) coating that is formed has and accelerate coking
Tendency.
This specification describes invention, including optimal mode with specific embodiment, and can help any
The people for being familiar with present invention process carries out experimental implementation.These operation include use any device and system and
Use the method for any materialization.The scope of the claims of the invention is defined by claims, and may be wrapped
Include example of other generations in the art.If described other examples in structure with claims
Written language without difference, or they have with claims describe suitable structure, all by
It is considered in the scope of claim of the invention.
Claims (13)
1. a kind of anti-coking coating, it includes anti-coking catalysis material and inorganic binder, wherein, institute
Stating inorganic binder includes phosphate, silicate, or combinations thereof.
2. anti-coking coating according to claim 1, wherein, the anti-coking catalysis material includes
Perovskite Phase related compounds, spinelle, carbonate, metal oxide, noble metal or their group
Close.
3. anti-coking coating according to claim 1, wherein, the anti-coking catalysis material includes
Chemical expression is An+1BnO3n+1Perovskite Phase related compounds, wherein, A be A material, including
At least one element selected from alkali metal, alkaline-earth metal and rare earth metal, B is B material, including extremely
A kind of few transition metal, O is oxygen, n >=1.
4. the anti-coking coating according to claim 3, wherein, A include Na, K, Ca,
Sr, Ba, La or combinations thereof, B include Mn, Co, Ni or combinations thereof.
5. anti-coking coating according to claim 1, wherein, the inorganic binder includes phosphoric acid
Aluminum dihydrogen, phosphoric acid hydrogen aluminium, aluminum phosphate, potassium silicate, sodium metasilicate or combinations thereof.
6. anti-coking coating according to claim 1, wherein, the inorganic binder includes phosphoric acid
Salt.
7. anti-coking coating according to claim 1, wherein, inorganic binder in the coating
Scope of the weight/mass percentage composition 1% to 90%.
8. a kind of product, it includes：
Metallic matrix；And
Anti-coking coating on the metallic matrix, the anti-coking coating include anti-coking catalysis material and
Inorganic binder, wherein the inorganic binder includes phosphate, silicate or combinations thereof.
9. product according to claim 8, it includes the table in INVENTIONLiquid-fueled combustion environment
Face, wherein the anti-coking coating is covered in the surface.
10. it is a kind of to protect the product in case it is due to the method exposed to fuel combustion environment and coking, its
Including：
The coating slurry on the product, the slurry includes anti-coking catalysis material and inorganic binder, its
In the inorganic binder include phosphate, silicate or combinations thereof；And
The product of slurry is coated with temperature below 900 DEG C described in roasting.
11. methods according to claim 10, wherein, the slurry further includes solvent, should
Solvent includes water, alcohols or combinations thereof.
12. methods according to claim 10, wherein, the slurry is by water-laid film technique
It is coated on the product.
13. methods according to claim 10, further include：Before the roasting, to described
The slurry being coated on product is dried.
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