CN106902831A - The catalysis material of anti-coking, the method for protecting product slagging prevention and the product for having anti-coking coating - Google Patents

The catalysis material of anti-coking, the method for protecting product slagging prevention and the product for having anti-coking coating Download PDF

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CN106902831A
CN106902831A CN201510977016.2A CN201510977016A CN106902831A CN 106902831 A CN106902831 A CN 106902831A CN 201510977016 A CN201510977016 A CN 201510977016A CN 106902831 A CN106902831 A CN 106902831A
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coking
coating
dopant
product
perovskite
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王世忠
傅琪佳
辛骞骞
张晓�
杰弗里·大卫·迈尔斯
曹雷
林川
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General Electric Co
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General Electric Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Inorganic Chemistry (AREA)
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Abstract

A kind of catalysis material of anti-coking, including expression formula is An+1BnO3n+1Perovskite-like compound.Wherein, A is A material, including at least one rare earth metal, and also including A dopant, the A dopant includes lithium, sodium, potassium, rubidium, caesium or combinations thereof；B is B material, including at least one magnesium-yttrium-transition metal, and O is oxygen, n >=1.A kind of surface in product coats the catalysis material in case the method for its coking by exposure to fuel combustion environment, and a kind of product for being coated with anti-coking coating.

Description

The catalysis material of anti-coking, the method for protecting product slagging prevention and the product for having anti-coking coating
Technical field
This invention relates generally to a kind of catalysis material of anti-coking, a kind of side of protection product slagging prevention Method and a kind of product for having an anti-coking coating.
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 de-coking operations 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.Such as, perovskite-like oxide La2NiO4It is a kind of known soot particulate matter burning Or oxidizing hydrocarbon catalysts, it is used for coke catalytic burning.Even if however, having La2NiO4 Presence, coke burning temperature it is still higher.
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 catalysis material of anti-coking includes that expression formula is An+1BnO3n+1Perovskite-like Compound.Wherein, A is A material, including at least one rare earth metal, also including A dopant, The A dopant includes lithium, sodium, potassium, rubidium, caesium or combinations thereof；B is B material, bag At least one magnesium-yttrium-transition metal is included, O is oxygen, n >=1.
On the other hand, a kind of surface for protecting product is in case it is by exposure to fuel combustion environment The method of coking, is included in the catalysis material that the surface coats anti-coking, and the catalysis material includes expression Formula is An+1BnO3n+1Perovskite-like compound.Wherein, A be A material, including at least one it is dilute Earth metal, also including A dopant, the A dopant include lithium, sodium, potassium, rubidium, caesium or it Combination；B is B material, including at least one magnesium-yttrium-transition metal, and O is oxygen, n >=1.
On the other hand, a kind of product includes the coating on metallic matrix and the metallic matrix, the coating bag Expression formula is included for An+1BnO3n+1Perovskite-like compound.Wherein, A is A material, including at least A kind of rare earth metal, also including A dopant, the A dopant include lithium, sodium, potassium, rubidium, caesium, Or combinations thereof；B is B material, including at least one magnesium-yttrium-transition metal, and O is oxygen, n >=1.
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：
Fig. 1 shows the LaNiO of the parallel testing in example 13、La0.95K0.05NiO3And La0.95Na0.05NiO3 The CO that catalysis combustion of coke is produced2Strength signal.
Fig. 2 shows the La of the parallel testing in example 22NiO4And La1.9K0.1NiO4Catalysis combustion of coke The CO of generation2Strength signal.
Fig. 3 shows the La of the parallel testing in example 32NiO4、La1.9Sr0.1NiO4And La1.9Sr0.2NiO4 The CO that catalysis combustion of coke is produced2Strength signal.
Fig. 4 shows the La of the parallel testing in example 42NiO4、La1.8Ba0.2NiO4、La1.6Ba0.4NiO4 And La1.3Ba0.7NiO4The CO that catalysis combustion of coke is produced2Strength signal.
Fig. 5 A show the La obtained in example two1.3K0.3Ba0.4NiO4The microstructure of base coating.
Fig. 5 B are shown in each circulation of crude oil oven test respectively obtained in example two La1.3K0.3Ba0.4NiO4The cinder weight that does not claim on cated bare board on base coating and at one Contrast.
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 directed to use with a kind of with good anticoking capability Perovskite Phase related compounds, its can be used as anti-coking catalysis material be coated on the metallic matrix of product with Form anti-coking coating.
The simplified expression of the Perovskite Phase related compounds is An+1BnO3n+1, wherein, A is to occupy A A material of position (oxygen tetrahedral interstice), B is to occupy B (oxygen octahedra gap) B material, O is oxygen, n >=1.The Perovskite Phase related compounds may include perovskite or perovskite-like oxide, Such as it is referred to as the laminated perovskite structure of Ruddlesden-Popper phases.Especially, when n tends to infinitely great When, acquisition is perovskite, and its simplified expression is ABO3.By lithium (Li), sodium (Na), potassium (K), Rubidium (Rb) or caesium (Cs) can be lifted to it as A dopant of the Perovskite Phase related compounds (i.e. carbonaceous material starts burning to the firing point of the carbonaceous materials such as the catalysis activity of coke burning, reduction carbon Minimum temperature), and/or the burning velocity for improving carbonaceous material.When the Perovskite Phase related compounds An+1BnO3n+1A include at least one rare earth element and it is a kind of include Li, Na, K, Rb, Cs or its A dopant of combination, and B is when including at least one transition metal, the burning of its STRENGTH ON COKE has fine Catalysis activity, the firing point of the carbonaceous materials such as carbon can be reduced, such as, fallen below from about 600 DEG C 400 DEG C or less than 300 DEG C.Therefore, it is burnt in the presence of the Perovskite Phase related compounds Charcoal or petroleum residue can be burnt at a lower temperature, even if thus fuel burning occur in phase To relatively low temperature, the Perovskite Phase related compounds still can use effectively to prevent coke build-up.
" rare earth metal " as herein described refers to the collection of the 17 elements composition in the periodic table of chemical element Close, including scandium (Sc), yttrium (Y), 15 group of the lanthanides and any combination of them.Wherein, described ten Five lanthanide series include 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 (Yb) and lutetium (Lu)." transition metal " as herein described is referred to three in the periodic table of chemical element To 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 La and A dopant, Wherein the A dopant includes Li, Na, K, Rb, Cs or combinations thereof.It is specific at some In embodiment, the expression formula An+1BnO3n+1In A include La and A dopant, the wherein A Position dopant includes Na, K or combinations thereof.In certain embodiments, the expression formula An+1BnO3n+1 In B include Mn, Co, Ni or combinations thereof.In some specific embodiments, the expression Formula An+1BnO3n+1In B include Ni.The example of some suitable Perovskite Phase related compounds includes La0.95K0.05NiO3、La0.95Na0.05NiO3、La1.9K0.1NiO4、La1.6K0.2Sr0.2NiO4With La1.3K0.3Ba0.4NiO4。
In certain embodiments, Mole percent of the A dopant in the total amount of the A material Content is no more than 99% more than 0%.In some specific embodiments, the A dopant is in institute State scope of the molar content in the A total amount of material about 0.5% to about 20%.
In actual use, generally coated the Perovskite Phase related compounds as anti-coking catalysis material In formation anti-coking coating on the metallic matrix of product.Because coating is generally close to the catalysis material Formed during fusing point, therefore for metallic matrix of the maximum tolerable temperature less than the catalysis material fusing point, The coating to form the catalysis material on its surface is extremely challenging.A kind of inorganic bond can be used Agent is combined together to form coating helping catalysis material.In certain embodiments, the coating is further Including a kind of inorganic binder, it can be at a temperature of less than the catalysis material fusing point on metallic matrix Form the coating of the catalysis material.There is the inorganic binder, catalysis material can be in relatively low temperature Under degree, such as at 600 DEG C or so, coating is formed on metallic matrix.Find a kind of suitable inorganic bond Agent, it can make the anticoking capability of catalyst keep good again for forming firm catalyst coatings, This is challenging.Need to may consider between binding agent and catalysis material and catalysis material and matrix it Between chemical compatibility.Furthermore, it is possible to also need the sintering temperature to binding agent species and concentration and coating Degree is designed, to avoid the catalysis activity to catalyst coatings from being 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 the content of quality hundred 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 Cover method (dip coating methods), spin coating method (spin coating methods), spraying process (spray Coating methods), mould cladding 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.In this example, prepare and Test the anti-scorch coating of heterogeneity.Unless otherwise mentioned, all of material or component can General chemical suppliers from the market are bought.
Example one
It is right in thermogravimetric analyzer (thermogravimetric analyzer, TGA) in example one The perovskite-like compound of different component is analyzed, to assess these perovskite-like compound STRENGTH ON COKEs The catalysis activity of burning.Each described perovskite-like compound is co-mulled and made into carbon black, to be ground altogether Mill mixture, then by the co-milled mixtures be put into thermogravimetric analyzer (purchased from Mettler-Toledo companies, Switzerland) in, it is placed in the flow velocity air containing 3% (molar content) moisture of about 80ml/ minutes, Be heated to about 10 DEG C/min of speed, such as, about 500 DEG C.In the process, the mixture In carbon black burning produce carbon dioxide (CO2).The mass spectrograph for being connected to the thermogravimetric analyzer (is purchased from Hiden Analytical companies, Warrington, Britain) it is used to measure the CO produced in thermogravimetric analyzer2 Intensity.The CO2Intensity indicates the catalysis activity of tested perovskite-like compound STRENGTH ON COKE burning. In each example of example 1 below -4, one group of change is abreast tested under substantially the same conditions Compound, to compare the catalysis activity of these compounds.
Example 1：Parallel testing simultaneously compares three kinds of perovskite LaNiO3、La0.95K0.05NiO3(K doping LaNiO3) and La0.95Na0.05NiO3(the LaNiO of Na doping3).These three measured in test process The CO that perovskite is obtained2Strength signal is shown in Fig. 1.As shown in figure 1, with no A dopant Perovskite (LaNiO3) compare, there is the perovskite of alkali metal such as potassium or natrium doping on A positions (La0.95K0.05NiO3And La0.95Na0.05NiO3) help to obtain carbon black burn rate higher.Additionally, Compared to LaNiO3For, La0.95K0.05NiO3And La0.95Na0.05NiO3Also so that the firing point reduction of carbon black About 50 DEG C.
Example 2：Parallel testing simultaneously compares two species perovskite compound La2NiO4And La1.9K0.1NiO4。 The CO that both the perovskite-like compounds measured in test process are obtained2Strength signal is shown in Fig. 2. As shown in Fig. 2 with without the A perovskite-like compound (La of dopant2NiO4) compare, in A There is the perovskite-like compound (La that potassium adulterates on position1.9K0.1NiO4) cause carbon black firing point reduce it is super Cross 50 DEG C.
Example 3：Parallel testing simultaneously compares three species perovskite compound La2NiO4、La1.9Sr0.1NiO4With La1.9Sr0.2NiO4.The CO that these three the perovskite-like compounds measured in test process are obtained2Intensity is believed Number it is shown in Fig. 3.As shown in figure 3, and La2NiO4Compare, there is alkaline-earth metal strontium to mix on A Miscellaneous perovskite-like compound (La1.9Sr0.1NiO4And La1.9Sr0.2NiO4) so that the firing point of carbon black is slightly Reduce.However, and La2NiO4Compare, La1.9Sr0.1NiO4And La1.9Sr0.2NiO4So that the burning of carbon black Rate reduction, and cause carbon black burn rate reduced with the increase of content of strontium, this show individually with Strontium has negative impact for perovskite-like compound for A dopant to the catalysis activity that carbon black burns.
Example 4：Parallel testing simultaneously compares four species perovskite compound La2NiO4、La1.8Ba0.2NiO4、 La1.6Ba0.4NiO4And La1.3Ba0.7NiO4.These four the perovskite-like compounds measured in test process are obtained The CO for obtaining2Strength signal is shown in Fig. 4.As shown in figure 4, and La2NiO4Compare, on A positions There is the perovskite-like compound (La that alkaline-earth metal barium adulterates1.8Ba0.2NiO4、La1.6Ba0.4NiO4With La1.3Ba0.7NiO4) without the firing point for reducing carbon black, the burn rate of carbon black is reduction of on the contrary, and And causing that carbon black burn rate is reduced with the increase of barium content, this shows to be individually A doping with barium Thing has negative impact for perovskite-like compound to the catalysis activity that carbon black burns.
The result of these examples shows, for perovskite-like compound, alkali metal is a kind of unique A doping, it is in terms of the burn rate of the firing point of carbon and/or lifting carbon is reduced compared with alkaline-earth metal There is the good of uniqueness.
Example two
In example two, to mix the perovskite-like compound L a of potassium1.3K0.3Ba0.4NiO4And inorganic adhesive Al·n(POx) for raw material is prepared for coating, then the coating is assessed.
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：By 0.5 gram of La1.3K0.3Ba0.4NiO4, Aln (the PO that prepare described in 0.15 gramx) Ethanol solution, 0.05 gram of n-butanol and the mixing of 0.38 gram of ethanol slurry is obtained.Will be obtained The method of slurry immersion coating is coated on metallic plate with the lifting speed of 100mm/min.It is coated with slurry The metallic plate of material is placed in air drying, obtains the metallic plate of band coating.Then dried at about 80 DEG C About 60 minutes, then dried about 60 minutes at about 260 DEG C again.Dried metallic plate is in atmosphere Roasting about 2 hours, sintering temperature is about 550 DEG C, and programming rate is about 2 DEG C/min.Such method is used, La can on a metal plate be formed1.3K0.3Ba0.4NiO4Base coating.
Microstructure and the adhesiveness analysis of coating：Observe described with SEM La1.3K0.3Ba0.4NiO4The microstructure of base coating.As shown in Figure 5A, the La1.3K0.3Ba0.4NiO4 Base coating has a small amount of crackle, but microscopic appearance is preferable.Also with survey adhesion standard adhesive tape method (ASTM D3359-B the adhesion of the coating) is measured, as a result finds that the coating has 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 La1.3K0.3Ba0.4NiO4Base is applied Crude oil is sprayed in the heat seal golden plate of layer, then the alloy sheets of crude oil that are coated with all are placed in batch-type furnace It is calcined at a temperature of 330 DEG C to 350 DEG C, the coking in the alloy sheets in the process can burn.Roasting Afterwards, to being coated with La1.3K0.3Ba0.4NiO4Cinder in the alloy sheets of base coating is weighed, with without The cinder weight claimed in the alloy sheets of coating is compared, to assess La1.3K0.3Ba0.4NiO4Base coating Anticoking capability.If the weight of the cinder claimed in the alloy sheets of band coating is less than not coated piece of conjunction The weight of the cinder claimed in golden plate, then the coating be considered as possessing anticoking capability.Claim in alloy sheets Cinder weight it is smaller, then the anticoking capability of coating is better.Wherein, it is described spraying and roasting be can It is repeated several times what is carried out, it is described if the process of once complete spraying and roasting is considered as into a circulation Crude oil roasting test may include multiple circulations.
Evaluating result：Fig. 5 B are shown in each circulation of crude oil oven test respectively described La1.3K0.3Ba0.4NiO4On base coating and in the cinder weight for and not claiming on cated bare board Contrast.The former cinder is significantly less weight than the latter as can be seen from Figure 5B, and this is indicated that, La1.3K0.3Ba0.4NiO4Base coating has good anticoking capability.
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 (12)

1. a kind of catalysis material of anti-coking, it includes that expression formula is An+1BnO3n+1Perovskite-like Compound, wherein, A is A material, including at least one rare earth metal, also including A dopant, The A dopant includes lithium, sodium, potassium, rubidium, caesium or combinations thereof, and B is B material, bag At least one magnesium-yttrium-transition metal is included, O is oxygen, n >=1.
2. anti-coking catalysis material as claimed in claim 1, wherein, A includes lanthanum and A is adulterated Thing, the A dopant includes sodium, potassium or combinations thereof, B include manganese, cobalt, nickel or they Combination.
3. anti-coking catalysis material as claimed in claim 1, wherein, A includes lanthanum and A is adulterated Thing, the A dopant includes sodium, potassium or combinations thereof, and B includes nickel.
4. anti-coking catalysis material as claimed in claim 1, wherein, the A dopant is relative 99% is less than more than 0% in the A molar content of material total amount.
5. anti-coking catalysis material as claimed in claim 4, wherein, the A dopant is relative In scope of the A molar content of material total amount 0.5% to 20%.
6. a kind of surface for protecting product is in case the side of its coking by exposure to fuel combustion environment Method, is included in the catalysis material that the surface coats anti-coking, and the catalysis material is including expression formula An+1BnO3n+1Perovskite-like compound, wherein, A is A material, including at least one rare earth is golden Category, also including A dopant, the A dopant including lithium, sodium, potassium, rubidium, caesium or they Combination, B is B material, including at least one magnesium-yttrium-transition metal, and O is oxygen, n >=1.
7. a kind of product, it includes：
Metallic matrix；And
Coating on the metallic matrix, the coating includes that expression formula is An+1BnO3n+1Perovskite-like Compound, wherein, A is A material, including at least one rare earth metal, also including A dopant, The A dopant includes lithium, sodium, potassium, rubidium, caesium or combinations thereof, and B is B material, bag At least one magnesium-yttrium-transition metal is included, O is oxygen, n >=1.
8. product as claimed in claim 7, wherein, the coating further includes inorganic adhesive, The inorganic adhesive includes phosphate, silicate or combinations thereof.
9. product as claimed in claim 8, wherein, the inorganic binder include aluminium dihydrogen phosphate, Phosphoric acid hydrogen aluminium, aluminum phosphate, potassium silicate, sodium metasilicate or combinations thereof.
10. product as claimed in claim 8, wherein, the inorganic adhesive includes phosphate.
11. products as claimed in claim 8, wherein, the inorganic adhesive is relative to the coating Scope of the mass percent 1% to 90%.
12. products as claimed in claim 7, including exposed to the surface of liquid fuel combustion environment, The coating is located at this on the surface of liquid fuel combustion environment.
CN201510977016.2A 2015-12-23 2015-12-23 The catalysis material of anti-coking, the method for protecting product slagging prevention and the product for having anti-coking coating Pending CN106902831A (en)

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Application publication date: 20170630