CN106905723A - The coating of anti-coking, the product for having anti-coking coating and the method for preventing product coking - Google Patents

Abstract

An anti-coking coating includes an anti-coking catalytic material and an inorganic binder, wherein the inorganic binder includes phosphate, silicate, or a combination thereof. An article covered with the anti-coking coating, and a method of protecting the article from coking due to exposure to a fuel combustion environment by the anti-coking coating.

Description

Anti-coking coating, article having anti-coking coating, and method of preventing article from coking

technical field

The present invention generally relates to an anti-coking coating, an article having an anti-coking coating, and a method of preventing coking of an article.

Background technique

Coking is a common phenomenon in liquid fuel or binary fuel combustion systems. For example, during the combustion of liquid fuels, coke may build up on the nozzle surfaces of gas turbines or engines. Due to the chemical decomposition of the fuel due to overheating in the nozzle and the long residence time of the fuel, internal coking may occur in the form of deposits of carbonaceous substances (ie coke deposits) on the fuel channels inside the nozzle. External coking or carbonization may also occur on the hot outer surfaces of the nozzles due to the deposition of carbonaceous species due to fuel distillation and/or liquid phase reactions occurring on the outer surfaces. Due to the build-up of coke, a layer of coke will gradually form on the surface of the nozzle, which may reduce the efficiency of the combustion system and even cause potential safety problems. Moreover, the accumulation of coke will adversely affect the physical properties of the nozzle, deteriorating mechanical properties such as enduring strength, cold and heat fatigue resistance, and ductility. Therefore, regular decoking is required. However, decoking can interrupt the production process and increase operating costs.

Various methods have been considered to eliminate the hazards caused by coke buildup on components such as gas turbine or engine nozzles. These methods include: from a metallurgical point of view, upgrading the metal base material of the nozzle; structural optimization of the dual-hole nozzle to overcome the problem of internal coking in the secondary fuel passage of the nozzle; selective pretreatment of the inner surface of the nozzle; the use of inert surface coating layer; catalytic gasification of coke to generate CO/CO ₂ and hydrogen.

Although some of the above-mentioned methods have been widely used in industry, people still expect a new method that can avoid or make up for the shortcomings of the above-mentioned methods, and can successfully reduce or eliminate coking.

Contents of the invention

In one aspect, an anti-coking coating includes an anti-coking catalytic material and an inorganic binder. Wherein, the inorganic binder includes phosphate, silicate, or a combination thereof.

In another aspect, an article includes a metal substrate and an anti-coking coating on the metal substrate. The anti-coking coating includes an anti-coking catalytic material and an inorganic binder. Wherein the inorganic binder includes phosphate, silicate or a combination thereof.

In another aspect, a method of protecting the article from coking due to exposure to a fuel combustion environment, comprising: coating the article with a slurry; and firing the coated slurry at a temperature below 900° C. Slurry products. The slurry includes an anti-coking catalytic material and an inorganic binder. Wherein the inorganic binder includes phosphate, silicate or their combination.

Description of drawings

These and other features, aspects and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings, in which like reference numerals are used to refer to like parts throughout, wherein :

FIG. 1A shows the microstructure of the La ₂ NiO ₄ -based coating obtained in Example 1.

Figure 1B shows a comparison of the weight of char residue weighed on the La2NiO4 _- based coating of Example ₁ and on an uncoated bare plate during each cycle of the crude oil roasting test.

Figure 2A shows the microstructure of the La _1.3 K _0.3 Ba _0.4 NiO ₄ -based coating obtained in Example 2.

Figure 2B shows the comparison of the weight of char residues weighed on the La _1.3 K _0.3 Ba _0.4 NiO ₄ -based coating of Example 2 and on an uncoated bare plate during each cycle of the crude oil roasting test.

Figure 3A shows the microstructure of the Sr _1.8 K _0.2 MnO ₄ -based coating obtained in Example 3.

Figure 3B shows the comparison of the weight of char residues weighed on the Sr _1.8 K _0.2 MnO ₄ -based coating of Example 3 and on an uncoated bare plate during each cycle of the crude oil roasting test.

Figure 4A shows the microstructure of the _SrCO3 -based coating obtained in Example 4.

Figure 4B shows a comparison of the weight of char residues weighed on the SrCO ₃ -based coating of Example 4 and on an uncoated bare plate during each cycle of the crude oil roasting test.

FIG. 5A shows the microstructure of the SrCO ₃ —NiO-based coating obtained in Example 5. FIG.

Figure 5B shows a comparison of the weight of char residues weighed on the _SrCO3 -NiO-based coating of Example 5 and on an uncoated bare panel in each cycle of the crude oil roasting test.

FIG. 6A shows the microstructure of the Al·n(PO _x ) coating obtained in Example 6. FIG.

Figure 6B shows a comparison of the weight of char residue weighed on the Al·n(PO _x ) coating of Example 6 and on an uncoated bare panel during each cycle of the crude oil roasting test.

detailed description

Unless otherwise defined, the technical terms or scientific terms used in the specification and claims shall have the ordinary meanings understood by those skilled in the technical field to which the present invention belongs. "First" or "second" and similar words used in the specification and claims do not indicate any order, quantity or importance, but are only used to distinguish different components. "A" or "one" and similar words do not indicate a limitation of number, but mean that there is at least one. Approximate language used herein may be used in quantitative terms, indicating that certain variations in quantities are permissible without changing essential function. Accordingly, values modified by language such as "about", "approximately" and the like are not limited to the exact value itself. In addition, in the expression "about the first value to the second value", "about" modifies both the first value and the second value. In some cases, the language of approximation may relate to the precision of the measuring instrument. Numerical values recited herein include all values in increments of one unit from the lower to the higher, provided that there is a separation of at least two units between any lower value and the higher value.

All the numerical values from the lowest value to the highest value listed in this article refer to all values obtained in increments of one unit between the lowest value and the highest value when the difference between the lowest value and the highest value is more than two units. value. For example, the number of components such as temperature, air pressure, time, etc., and the value of the process, etc. When we say 1 to 90, we mean, for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc. enumeration value. When the value is less than 1, one unit can be 0.0001, 0.001, 0.01, or 0.1. Here is just a special example to illustrate. The numbers listed in this article refer to all possible numerical combinations between the maximum value and the minimum value obtained by similar methods.

Embodiments of the present invention relate to methods of reducing or eliminating coke buildup on metal articles used in fuel, particularly liquid fuel and binary fuel combustion environments, for example, gas turbine or engine liquid fuel combustion environments. The method involves coating an anti-coking catalytic material on a metal substrate of an article to form a catalytic coating with good anti-coking properties. The anti-coking catalytic material can reduce the light-off point of carbonaceous materials such as carbon (ie, the lowest temperature at which carbonaceous materials start to burn), for example, from about 600°C to lower than 400°C or lower than 300°C, and/or Increase the burning speed of carbonaceous materials. Therefore, in the presence of the catalytic material, the coke or petroleum residue can be combusted at a lower temperature and/or a higher combustion rate, so that even if the fuel combustion occurs at a relatively low temperature, it can still be Effectively prevent coke accumulation.

The anti-coking catalytic material may be any suitable material that has catalytic activity for coke combustion and can reduce the ignition point of carbonaceous materials such as carbon and/or increase the burning speed of carbonaceous materials. Some examples of coking-resistant catalytic materials include, but are not limited to, perovskite-related compounds, spinels, carbonates, noble metals.

The "perovskite-related compound" described herein refers to a compound whose simplified expression is A _a B _b O _o , where A is the A-site material occupying the A-site (oxygen tetrahedral gap), and B is the A-site material occupying the B-site ( Oxygen octahedral interstitial) B-site material, O is oxygen, and a, b and o represent the stoichiometric numbers of the corresponding elements that can make the compound have a single phase. The "spinel" described herein refers to a compound whose simplified expression is XY ₂ O ₄ (X ²⁺ Y ³⁺ ₂ O ^2- ₄ ). This simplifies compounds of the general formula. Although in a typical spinel structure, X and Y are +2 and +3, respectively, in practice, monovalent, divalent, trivalent or tetravalent cations such as potassium, magnesium, aluminum, iron, zinc Combinations of , manganese, chromium, silicon are also possible.

In some embodiments, the anti-coking catalytic material includes a perovskite-related compound with a simplified expression of A _n+1 B _n O _3n+1 , where A is the A-site occupying the A-site (oxygen tetrahedral gap) Material, B is the material occupying the B site (oxygen octahedral gap), O is oxygen, and n≥1. The perovskite-related compounds may include perovskites, or perovskite-like oxides, such as layered perovskite structures known as Ruddlesden-Popper phases. In particular, when n tends to infinity, a perovskite is obtained, whose simplified expression is ABO ₃ . In some embodiments, the A-site material or the B-site material may include at least one element selected from alkali metals, alkaline earth metals, rare earth metals, and transition metals. In some specific embodiments, the A-site material includes at least one element selected from alkali metals, alkaline earth metals and rare earth metals. The B-site material includes at least one transition metal.

"Alkali metals" as used herein refers to the elements of the first main group of the periodic table of chemical elements (International Union of Theoretical and Applied Chemistry, IUPAC), including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), Cesium (Cs) and Francium (Fr). The term "alkaline earth metal" as used herein refers to the elements of the second main group in the periodic table of chemical elements, including beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium ( Ra). As used herein, "rare earth metals" refers to the set of seventeen elements in the periodic table of chemical elements, including scandium (Sc), yttrium (Y), fifteen lanthanides, and any combination thereof. Wherein, the fifteen lanthanides 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 metals" as used herein refer to the chemical elements of the periodic table Elements of the three to twelve main groups in the medium, 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 (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au) , Mercury (Hg).

In some embodiments, A in the expression A _n+1 B _n O _3n+1 includes Na, K, Ca, Sr, Ba, La or combinations thereof. In some specific embodiments, A in the expression A _n+1 B _n O _3n+1 includes La, and optionally includes a dopant including Na, K, Ca, Sr, Ba or their combination. In some embodiments, B in the expression A _n+1 B _n O _3n+1 includes Mn, Co, Ni or a combination thereof. In some specific embodiments, B in the expression A _n+1 B _n O _3n+1 includes Ni. Some examples of suitable perovskite-related compounds include LaNiO ₃ , La _0.9 Sr _0.1 NiO ₃ , La ₂ NiO ₄ , La _1.9 K _0.1 NiO ₄ , La _1.9 Na _0.1 NiO ₄ , LaSrNiO ₄ , Sr ₂ MnO ₄ , Sr _1.8 K _0.2 MnO ₄ and La _1.3 K _0.3 Ba _0.4 NiO ₄ .

Since the coating is usually formed close to the melting point of the catalytic material, it is extremely challenging to form a coating of the catalytic material on the surface of a metal substrate whose maximum withstand temperature is lower than the melting point of the catalytic material sexual. An inorganic binder may be used to help bind the catalytic materials together to form the coating. In some embodiments, the coating further includes an inorganic binder capable of forming a coating of the catalytic material on the metal substrate at a temperature below the melting point of the catalytic material. With the inorganic binder, the catalytic material can form a coating on the metal substrate at a relatively low temperature, such as around 600°C. It is challenging to find a suitable inorganic binder that can be used to form a robust catalytic coating while maintaining good coking resistance of the catalyst. Chemical compatibility between the binder and the catalytic material and between the catalytic material and the substrate may need to be considered. In addition, the type and concentration of the binder, as well as the sintering temperature of the coating, may need to be designed to avoid negative effects on the catalytic activity of the catalytic coating.

In some embodiments, the inorganic binder includes phosphates, silicates, or combinations thereof. In some specific embodiments, the inorganic binder includes phosphate. "Phosphate" as used herein refers to inorganic compounds including phosphate anion PO _x , such as PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ^— . " ^Silicate " refers to inorganic compounds that include silicate anions _SiOx , such as _SiO32- and ^SiO44- _. In some specific embodiments, the inorganic binder includes aluminum dihydrogen phosphate (Al(H ₂ PO ₄ ) ₃ ), aluminum hydrogen phosphate (Al ₂ (HPO ₄ ) ₃ ), aluminum phosphate ( Al·n( PO _x ) ), potassium silicate (K-Si-O, such as K ₂ SiO ₃ or K ₄ SiO ₄ ), sodium silicate (Na-Si-O, such as Na ₂ SiO ₃ or Na ₄ SiO ₄ ), or their combination. With said inorganic binders, anti-coking coatings with good homogeneity and mechanical properties can be obtained at relatively low temperatures. In addition, the inorganic binder in the coating does not accelerate the deposition of coke, so that the coating can guarantee good catalytic activity.

In some embodiments, the mass percentage of the inorganic binder relative to the coating is in the range of about 1% to about 90%, and the mass percentage of the catalytic material relative to the coating is in the range of about 10% to About 99% range.

Embodiments of the present invention also relate to a method of protecting an article from coking due to exposure to a fuel combustion environment by forming said anti-coking coating on the article. In this method, the catalytic material and the inorganic binder can be used to prepare a slurry, and then the slurry is coated by a suitable coating process or method, such as a wet-chemical deposition process. Applied on the article, such as coating on the surface of the article to be exposed to the combustion environment of liquid fuel. The slurry-coated article may be dried to obtain a coated article. The coated article may be fired or sintered. This forms an anti-coking coating on the substrate of the article. In some embodiments, the firing or sintering is performed at a relatively low temperature, such as below 900°C. In some specific embodiments, the calcination or sintering is performed at a temperature ranging from 300°C to 900°C, or further, at a temperature ranging from 300°C to 600°C.

As used herein, "slurry" refers to a fluid mixture of solids (usually solid powders) and liquids. The properties of the slurry can be similar to viscous liquids, can flow under the action of gravity, and can be pumped if it is not very viscous. "Wet-chemical deposition" refers to a coating method based on liquid-state operation, which involves applying a liquid precursor layer on a substrate, and then converting the liquid precursor layer into the desired coating through subsequent processing. Floor. Some examples of wet film forming processes include dip coating methods, spin coating methods, spray coating methods, die coating methods, screen printing methods (screen printing methods).

The slurry may further include a solvent. The solvent may include water, alcohols, or combinations thereof. Examples of some suitable alcohols include methanol, ethanol and n-butanol. In some embodiments, the inorganic binder includes K ₂ SiO ₃ or Na ₂ SiO ₃ , and the solvent includes water. In some embodiments, the inorganic binder includes phosphate, such as Al·n(PO _x ), and the solvent includes alcohols. In some embodiments, the mass percentage of the anti-coking catalytic material in the slurry is in the range of about 30% to about 60%, and the mass percentage of the inorganic binder in the slurry is The content ranges from about 2% to about 15%. The slurry may further include a dispersant for increasing the dispersion of solid particles in the slurry. The slurry may further include an organic binder such as polyvinyl butyral (PVB). In the subsequent process of forming the coating, the organic matter in the slurry, such as the solvent, the dispersant and/or the organic binder, may be burned out, depending on the process of forming the coating. The temperature reached by the slurry.

Embodiments of the invention also relate to an article covered with the aforementioned anti-coking coating. The foregoing article may comprise a metal substrate and an anti-coking coating as previously described applied to the metal substrate. The metal matrix may be made of any suitable metal or alloy, including but not limited to iron-based alloys, cobalt-based alloys, nickel-based alloys, or combinations thereof. The anti-coking coating can be of a suitable thickness generally required to obtain anti-coking properties. In some embodiments, the anti-coking coating has a thickness of about 1-200 microns. The anti-coking coating can be formed by the aforementioned process. Said article may be any component having a surface exposed to a liquid fuel or binary fuel combustion environment, and said anti-coking coating is applied to at least said surface exposed to a liquid fuel or binary fuel combustion environment. In some embodiments, the article is a nozzle for a gas turbine or engine, the nozzle having at least one surface exposed to a liquid fuel combustion environment.

Embodiments of the invention are illustrated by reference to some non-limiting examples. The following examples are intended to explain in detail to those skilled in the art how to evaluate the materials and methods described in the claims, and should not be viewed as limiting the present invention from any angle.

example

In this example, anti-scorch coatings of different compositions were prepared and tested. Unless otherwise specified, all materials or components were obtained from commercially available chemical suppliers.

Preparation of Al·n(PO _x ) : 88 grams of aluminum nitrate nonahydrate (H ₁₈ AlN ₃ O ₁₈ ) was dissolved in 79 grams of ethanol by ultrasonic treatment to obtain an ethanol solution of H ₁₈ AlN ₃ O ₁₈ . 33 grams of phosphorus pentoxide was dissolved in 105 grams of ethanol by ultrasonic treatment to obtain an ethanol solution of phosphorus pentoxide. The two solutions were mixed to obtain a mixed solution, and the mixed solution was refluxed for about 5 hours, and then cooled to room temperature to obtain an ethanol solution of Al·n(PO _x ).

Preparation of Coatings: Coating slurries were prepared using the formulations in Table 1 below. In Example 1, a slurry was prepared by mixing 0.1 gram of La ₂ NiO ₄ , 0.1 gram of sodium silicate (522-T, available from Aremco Products Company, New York), and 1 gram of water. In Example 2, a slurry was prepared by mixing 0.5 g of La _1.3 K _0.3 Ba _0.4 NiO ₄ , 0.15 g of the prepared Al·n(PO _x ) ethanol solution, 0.05 g of n-butanol and 0.38 g of ethanol material. In Example 3, 1.0 gram of Sr _1.8 K _0.2 MnO ₄ , 0.3 gram of the prepared Al·n(PO _x ) ethanol solution, 1.0 gram of ethanol, 0.1 gram of polyvinyl butyral containing 8 wt% A solution of (PVB) in ethanol (where PVB is used as an organic binder and ethanol as a part of the solvent) and 0.2 g of Disperbyk-110 dispersant (purchased from BYK Additives & Instruments) were mixed to prepare a slurry. In Example 4, 2.0 grams of SrCO ₃ , 0.6 grams of the prepared Al·n(PO _x ) ethanol solution, 0.2 grams of 8wt% PVB-containing ethanol solution, and 0.4 grams of Disperbyk-110 dispersant were mixed to prepare the slurry. In Example 5, 0.44 g of SrCO ₃ , 0.16 g of NiO, 0.2 g of the prepared Al·n(PO _x ) ethanol solution, 0.6 g of ethanol, 0.06 g of 8wt% PVB-containing ethanol solution, and 0.1 g Disperbyk-110 dispersant was mixed to make the slurry. In Example 6, the prepared Al·n(PO _x ) ethanol solution was directly used as the slurry without adding an anti-coking catalyst.

Each of the prepared slurries was applied separately to a metal plate to make a coating. What used in example 1 is the method of spraying. What Example 2 and 3 used was the method of dip coating, and the lifting speed was 100mm/min. Each slurry-coated metal panel was left to air dry to obtain a coated metal panel. This is followed by drying at about 80°C for about 60 minutes and then at about 260°C for about 60 minutes. The dried metal plate is calcined in the air for about 2 hours, the calcining temperature is about 550°C, and the heating rate is about 2°C/min. With such a method, La ₂ NiO ₄ base coating can be obtained on the metal plate of example 1; La _1.3 K _0.3 Ba _0.4 NiO ₄ base coating can be obtained on the metal plate of example 2; Sr can be obtained on the metal plate of example 3 _1.8 K _0.2 MnO ₄ -based coating; SrCO ₃ -based coating can be obtained on the metal plate of Example 4; SrCO ₃ -NiO-based coating can be obtained on the metal plate of Example 5; Al·n (PO _x ) coating (no catalyst).

Table I

Microstructure and Adhesion Analysis of Coatings: The microstructures of the coatings obtained in Examples 1 to 6 were observed with a scanning electron microscope. The microstructure of the _{La2NiO4 -} based coating is shown in Figure 1A, and it can be seen from Figure 1A that the _{La2NiO4 -} based coating is dense and crack-free. The La _1.3 K _0.3 Ba _0.4 NiO ₄ based coating is shown in Fig. 2A, and it can be seen from Fig. 2A that the La _1.3 K _0.3 Ba _0.4 NiO ₄ based coating has some cracks. The _{microstructure} of the _{Sr1.8K0.2MnO4 -} based coating is shown in Fig. 3A. It can be seen from Fig. 3A that the Sr _1.8 K _0.2 MnO ₄ based coating also has some cracks. The microstructure of the _SrCO3 -based coating is shown in Fig. 4A. From Figure 4A, it can be seen that the _SrCO3 -based coating is dense and crack-free. The microstructure of the SrCO ₃ -NiO based coating is shown in Fig. 5A. It can be seen from Fig. 5A that the _SrCO3 -NiO based coating is also dense and crack-free. The microstructure of the Al·n(PO _x ) coating is shown in Figure 6A, and it can be seen from Figure 6A that the Al·n(PO _x ) coating has cracks. In addition, the adhesion of each coating was measured using the standard adhesive tape method (ASTM D3359-B). All six coatings were found to have an excellent adhesion rating of 4-5B.

Crude oil roasting test : The crude oil roasting test is used to simulate the combustion process of liquid fuels. In this test, crude oil is sprayed on the bare hot alloy plate (without coating) and on the hot alloy plate covered with the coating to be tested (sample 1, 2, 3, 4, 5 or 6). The alloy plate sprayed with crude oil is placed in a box furnace and fired at a temperature of 330° C. to 350° C., during which coking on the alloy plate will burn. After firing, weigh the coke slag on the alloy plate covered with the coating to be tested, and compare it with the weight of the coke slag on the alloy plate without coating to evaluate the anti-coking performance of the coating to be tested. A coating is considered to be resistant to coking if the weight of char residue weighed on the coated alloy plate is less than the weight weighed on the uncoated alloy plate. The smaller the weight of the coke slag weighed on the alloy plate, the better the anti-coking performance of the coating. Wherein, the spraying and roasting can be repeated many times. If a complete spraying and roasting process is regarded as a cycle, the crude oil roasting test can include multiple cycles.

Evaluation results : Figure 1B shows the comparison of the weight of coke on the La ₂ NiO ₄ -based coating obtained in Example 1 and on the bare plate without coating in each cycle of the crude oil roasting test. It can be seen from Figure 1B that the weight of the former is much smaller than that of the latter, which indicates that the La ₂ NiO ₄ -based coating has good anti-coking performance.

Figure 2B shows the comparison of the weight of char residues weighed on the La _1.3 K _0.3 Ba _0.4 NiO ₄ -based coating obtained in Example 2 and on the bare plate without coating in each cycle of the crude oil roasting test. It can be seen from Figure 2B that the weight of the former is much smaller than that of the latter, which indicates that the La _1.3 K _0.3 Ba _0.4 NiO ₄ based coating has good anti-coking performance.

Fig. 3B shows the comparison of the weight of char residue on the Sr _1.8 K _0.2 MnO ₄ -based coating obtained in Example 3 and on the bare plate without coating in each cycle of the crude oil roasting test. It can be seen from Figure 3B that the weight of the former is much smaller than that of the latter, which indicates that the Sr _1.8 K _0.2 MnO ₄ -based coating has good anti-coking performance.

Figure 4B shows the comparison of the weight of char residues weighed on the _SrCO3 -based coating obtained in Example 4 and on the bare plate without coating in each cycle of the crude oil roasting test. It can be seen from Figure 4B that the weight of the former is much smaller than that of the latter, which indicates that the SrCO ₃ -based coating has good anti-coking performance.

Fig. 5B shows the comparison of the weight of char residue obtained on the _SrCO3 -NiO mixture-based coating obtained in Example 5 and on the bare plate without coating in each cycle of the crude oil roasting test. It can be seen from Fig. 5B that the coke residue weight of the former is much smaller than that of the latter, which indicates that the SrCO ₃ -NiO mixture-based coating has good anti-coking performance.

Figure 6B shows the comparison of the weight of char residues weighed on the Al·n(PO _x ) coating obtained in Example 6 and on the uncoated bare plate in each cycle of the crude oil roasting test. It can be seen from Fig. 6B that the weight of the former is much larger than that of the latter, which indicates that the coating formed solely with Al·n(PO _x ) tends to accelerate coking.

This specification describes the invention with specific embodiments, including the best mode, and can help anyone familiar with the technology of the invention to perform experimental operations. These operations include using any devices and systems and employing any embodied method. The patentable scope of the invention is defined by the claims, and may include other examples that occur within the technical field. Such other examples are intended to be within the scope of the claims if they do not differ in structure from the literal language of the claims, or if they have structures equivalent to those described in the claims.

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 A_n+1B_nO_3n+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.