Detailed Description
The invention provides a high-temperature oxygen-deficient catalytic combustion catalyst, which comprises a carrier with a mesoporous structure and a noble metal active component loaded in the carrier with the mesoporous structure;
the carrier with the mesoporous structure is CeO2-ZrO2@ HMS; the CeO2-ZrO2@ CeO in HMS2-ZrO2Doped with yttrium oxide and lanthanum oxide;
the noble metal active component is Ru and Pt.
In the present invention, the CeO2-ZrO2@ CeO in HMS2-ZrO2Dispersed in the mesoporous structure of HMS; the noble metal active component and the cocatalyst are loaded on the CeO2-ZrO2Of (2) is provided.
In the invention, the high-temperature oxygen-deficient catalytic combustion catalyst comprises a carrier with a mesoporous structure, and the carrier with the mesoporous structure is CeO2-ZrO2@ HMS; the CeO2-ZrO2@ CeO in HMS2-ZrO2Doped with yttrium oxide and lanthanum oxide. In the invention, the HMS is preferably a hexagonal mesoporous silica molecular sieve; the CeO2-ZrO2Preferably CeO2And ZrO2The solid solution composite of (1).
In the present invention, CeO2-ZrO2@ CeO in HMS2And ZrO2The total mass of the catalyst is preferably 36-60% by mass, more preferably 43.7-51.3% by mass, even more preferably 45-49.6% by mass, and most preferably 46.5-47.2% by mass; the CeO2And ZrO2The mass ratio of (1) to (3) is preferably (18-30): (18-30), more preferably (21.9-25.7): (21.9 to 25.7), more preferably (22.3 to 24.5): (22.5-25.1), most preferably (23.1-24.2): (23.4-25). In the invention, the mass percentage content of the yttrium oxide in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 0.5-5%, more preferably 1.0-4.0%, and most preferably 2.0-3.0%; the yttrium oxide is preferably yttrium oxide; the mass percentage content of the lanthanum oxide in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 0.5-5%, more preferably 1.0-4.0%, and the most preferable isPreferably 2.0 to 3.0 percent; the lanthanum oxide is preferably lanthanum trioxide.
In the present invention, the CeO2-ZrO2The mass percentage content of HMS in the @ HMS in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 30-45%, more preferably 38-42%, and most preferably 40%.
In the present invention, the high-temperature oxygen-deficient catalytic combustion catalyst further comprises a noble metal active component supported in the carrier having a mesoporous structure; the noble metal active component is Ru and Pt. In the invention, the mass percentage content of Pt in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 0.05-0.3%, more preferably 0.08-0.21%, and most preferably 0.13-0.16%; the mass percentage content of Ru in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 0.1-0.8%, more preferably 0.2-0.6%, and most preferably 0.3-0.5%.
In the present invention, the high-temperature anoxic catalytic combustion catalyst further preferably includes a promoter component supported in the support having a mesoporous structure; the promoter component is preferably an Mn oxide and/or a Co oxide; when the cocatalyst is Mn oxide and Co oxide, the invention has no special limitation on the proportion of the Mn oxide and the Co oxide, and the Mn oxide and the Co oxide can be mixed according to any proportion. In the present invention, the manganese oxide is preferably manganese dioxide; the cobalt oxide is preferably tricobalt tetraoxide. In the invention, the mass percentage content of the cocatalyst in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 8-14%, and more preferably 10-12%. In a specific embodiment of the present invention, the mass ratio of the Mn oxide to the Co oxide is specifically 7.5:3.5, 5.5:4.5, 6:5.5, 5:5, 6:4, 5:3, or 7: 6.
In the invention, the cocatalyst can enhance the oxygen activation capability of the catalyst, and the catalytic activity and the carbon deposit resistance capability of the high-temperature oxygen-deficient catalytic combustion catalyst are enhanced by virtue of the synergistic effect of the cocatalyst and the noble metal catalytic active component.
The invention also provides a preparation method of the high-temperature oxygen-deficient catalytic combustion catalyst, which comprises the following steps:
mixing soluble cerium salt, soluble zirconium salt, soluble yttrium salt, soluble lanthanum salt, urea and water, sequentially carrying out heating homogeneous precipitation reaction and first hydrothermal reaction, and carrying out first roasting on the obtained precipitation product to obtain a first carrier product;
mixing the first carrier product, water, ethyl acetate, citric acid, soluble noble metal salt and hydrazine hydrate, and carrying out reduction reaction to obtain a first dispersion product; the soluble noble metal salt comprises soluble ruthenium salt and/or soluble platinum salt;
mixing dodecylamine, the first dispersion product, a solvent and ethyl orthosilicate, performing polymerization self-assembly, adding soluble salt corresponding to a cocatalyst, and sequentially performing deep polymerization self-assembly and second roasting to obtain Pt-Ru-CeO2-ZrO2@ Co-Mn-HMS; the soluble salt corresponding to the cocatalyst comprises a soluble manganese salt and/or a soluble cobalt salt;
subjecting the Pt-Ru-CeO2-ZrO2Mixing the @ Co-Mn-HMS and water, and sequentially carrying out a second hydrothermal reaction and third roasting to obtain the high-temperature anoxic catalytic combustion catalyst.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing soluble cerium salt, soluble zirconium salt, soluble yttrium salt, soluble lanthanum salt, urea and water, sequentially carrying out heating homogeneous precipitation reaction and first hydrothermal reaction, and carrying out first roasting on the obtained precipitation product to obtain a first carrier product.
The soluble cerium salt, the soluble zirconium salt, the soluble yttrium salt and the soluble lanthanum salt are not particularly limited in kind, and those known to those skilled in the art can be used. In a specific embodiment of the present invention, the soluble cerium salt, the soluble zirconium salt, the soluble yttrium salt and the soluble lanthanum salt are, in order, specifically cerium nitrate, zirconium nitrate, yttrium nitrate and lanthanum nitrate.
In the invention, the mass ratio of the soluble cerium salt, the soluble zirconium salt, the soluble yttrium salt and the soluble lanthanum salt is preferably (1-2): (1-2): (0.03-0.3): (0.03-0.15), more preferably (1.2-1.8): (1.2-1.8): (0.04-0.09): (0.04-0.09), most preferably (1.4-1.6): (1.4-1.6): (0.05-0.07): (0.05-0.07).
In the present invention, the ratio of the amount of the substance of urea to the total amount of substance of cerium in the soluble cerium salt, zirconium in the soluble zirconium salt, yttrium in the soluble yttrium salt and lanthanum in the soluble lanthanum salt is preferably 5: 1.
In the invention, the urea is used as a precipitator, the urea is heated to 90 ℃ and decomposed to uniformly release ammonia gas, and then the ammonia gas is uniformly precipitated to obtain CeO2-ZrO2And further is beneficial to controlling the formation of the CeO with uniform size2-ZrO2The nano particles are beneficial to coating the HMS during the subsequent synthesis of the HMS.
In the present invention, the mass ratio of the soluble cerium salt to water is preferably (0.5 to 2): 10, more preferably (0.7 to 1.5): 10, most preferably 0.9: 10. in the present invention, the mixing preferably comprises the steps of: mixing soluble cerium salt, soluble zirconium salt, soluble yttrium salt, soluble lanthanum salt and water to obtain mixed metal salt solution; mixing the mixed metal salt solution with urea.
In the invention, the temperature of the heating homogeneous precipitation reaction is preferably 90-95 ℃, more preferably 91-94 ℃, and most preferably 92-93 ℃; the time is preferably 2 to 5 hours, and more preferably 3 to 4 hours.
The product system obtained after the heating homogeneous precipitation reaction is completed is preferably a suspension containing a precipitate, and the invention preferably performs a first hydrothermal reaction on the obtained suspension containing the precipitate.
In the invention, the temperature of the first hydrothermal reaction is preferably 120-150 ℃, and more preferably 130-140 ℃; the time is preferably 12 to 24 hours, and more preferably 15 to 20 hours.
After the hydrothermal reaction is finished, the method also preferably comprises the steps of filtering, washing and drying which are sequentially carried out; the filtration, washing and drying processes of the present invention are not particularly limited, and may be performed by processes well known to those skilled in the art. In the specific embodiment of the invention, the washing is preferably performed 3-6 times by using deionized water; the drying is drying at 80 ℃ for 6 h.
In the invention, the temperature of the first roasting is preferably 680-800 ℃, more preferably 690-740 ℃, and most preferably 700-730 ℃; the time is 2 h.
In the present invention, the first carrier product is specifically CeO doped with yttrium oxide and lanthanum oxide2-ZrO2。
After a first carrier product is obtained, mixing the first carrier product, water, ethyl acetate, citric acid, soluble noble metal salt and hydrazine hydrate to perform a reduction reaction to obtain a first dispersion product; the soluble noble metal salt comprises a soluble ruthenium salt and/or a soluble platinum salt.
The soluble ruthenium salt and the soluble platinum salt are not particularly limited in kind in the present invention, and those known to those skilled in the art can be used. In a specific embodiment of the invention, the soluble ruthenium salt is specifically ruthenium chloride; the soluble platinum salt is specifically H14Cl6O6Pt。
In the present invention, the ethyl acetate acts to disperse the solids, increasing viscosity; the citric acid acts as a complexing metal salt, improving its dispersion.
In the present invention, the mass ratio of the first carrier product, water, ethyl acetate and citric acid is preferably 1: (0.2-0.5): (0.1-0.5): (0.5 to 1), more preferably 1: (0.3-0.4): (0.2-0.3): (0.6-0.8).
In the present invention, the mass ratio of the first carrier product and the soluble noble metal salt is preferably 80: (0.06-0.9), more preferably 80: (0.13 to 0.52), most preferably 80: (0.26 to 0.33); the mass of the soluble noble metal salt is based on the mass of the noble metal. When the soluble precious metal salt is soluble ruthenium salt and soluble platinum salt, the mass ratio of a ruthenium metal simple substance in the soluble ruthenium salt to a platinum metal simple substance in the soluble platinum salt is preferably (0.05-0.4): (0.05-0.3), more preferably (0.08-0.21): (0.08-0.21), most preferably (0.13-0.18): (0.13-0.18).
In the present invention, the molar ratio of the noble metal and hydrazine hydrate in the soluble noble metal salt is preferably 1: (1.5 to 5.5), more preferably 1: (1.8 to 3.2), most preferably 1: (2.1-2.6).
In the present invention, the process of mixing preferably comprises the steps of: mixing the first carrier product, water, ethyl acetate and citric acid, and performing ball milling to obtain a turbid liquid; and sequentially adding soluble noble metal salt and hydrazine hydrate into the turbid solution. In the invention, the temperature of the mixing ball mill is preferably room temperature, the rotating speed is preferably 500-1000 rpm/min, and more preferably 600-800 rpm/min; the time is preferably 10 to 30min, more preferably 15 to 25min, and most preferably 18 to 22 min. In the present invention, the addition of the soluble noble metal salt and hydrazine hydrate is preferably carried out under stirring, and the stirring process for the fluorine of the present invention is not particularly limited, and may be carried out under conditions well known to those skilled in the art.
In the invention, the temperature of the reduction reaction is preferably room temperature, and the time is preferably 15-30 min.
After the reduction reaction is completed, the obtained product system is preferably filtered, and the filtration is carried out by adopting a process well known to a person skilled in the art without any special limitation and can ensure that solid-liquid separation is realized.
After the filtration is completed, the present invention preferably disperses the solid obtained by the filtration in anhydrous ethanol to obtain a first dispersion product. In the present invention, the solid content of the first dispersion product is preferably 10 to 60%, more preferably 20 to 50%, and most preferably 45%.
In the present invention, the dispersoid in the product obtained by the reduction reaction, i.e., the first dispersion product, is Pt-Ru-CeO2-ZrO2。
After the first dispersion product is obtained, the invention mixes the dodecylamine, the first dispersion product, the solvent and the tetraethoxysilane, carries out polymerization reaction self-assembly, and adds the cocatalystSequentially carrying out deep polymerization reaction self-assembly and second roasting on soluble salt corresponding to the reagent to obtain Pt-Ru-CeO2-ZrO2@ Co-Mn-HMS; the corresponding soluble salt of the promoter comprises soluble manganese salt and/or soluble cobalt salt.
In the present invention, the solvent is preferably a mixed solution of ethanol and water; the volume ratio of the ethanol to the water is preferably 1-8: 1, more preferably 5: 1.
In the invention, the mass ratio of the dodecylamine to the ethyl orthosilicate is preferably (1-5): (2-8), more preferably (2-3): (5-6). In the invention, the volume ratio of the dodecylamine to the solvent is preferably (5-30): 500, more preferably (6-15): 500. in the present invention, the volume of the dodecylamine is preferably the volume of a dodecylamine liquid obtained after heating dodecylamine.
In the invention, the mass ratio of the first dispersion product, the ethyl orthosilicate and the soluble salt corresponding to the promoter is preferably (36.15-61.5): (105-158): (8-20), more preferably (40-58): (125-150): (9-13), most preferably (45-52): (133-142): (10-12); the soluble salt corresponding to the cocatalyst is calculated by the oxide corresponding to the cocatalyst.
In the invention, the dodecylamine is used as a template agent for synthesizing HMS, and the tetraethoxysilane is used as a raw material for preparing HMS.
In the present invention, the mixing of the dodecylamine, the first dispersion product, the solvent and the ethyl orthosilicate is preferably performed by adding the first dispersion product and the ethyl orthosilicate after mixing the dodecylamine and the solvent. In the present invention, the mixing is preferably performed at room temperature under stirring. In the present invention, the stirring time is preferably 3 hours. In the present invention, the addition manner of the tetraethoxysilane is preferably dropwise.
In the present invention, the temperature of the polymerization self-assembly is preferably room temperature; the time is preferably 1 h. In the present invention, the time is based on the time when the addition of tetraethoxysilane is completed as the starting time.
In the invention, the soluble salts corresponding to the cocatalyst comprise soluble manganese salt and soluble cobalt salt; when the soluble salt corresponding to the cocatalyst is soluble manganese salt and soluble cobalt salt, the molar ratio of the soluble manganese salt to the soluble cobalt salt is preferably (1-4): (1-4), more preferably (2-3): (2-3). In a specific embodiment of the present invention, the soluble manganese salt is specifically manganese nitrate, and the soluble cobalt salt is specifically cobalt nitrate.
In the invention, the oxide corresponding to the cocatalyst accounts for 8-14% of the mass of the catalyst.
In the invention, the temperature of the deep polymerization self-assembly is preferably room temperature, and the time is preferably 10-30 h, more preferably 15-25 h, and most preferably 20 h. In the present invention, the deep polymerization self-assembly is preferably carried out under stirring conditions; the rotation speed of the stirring is not limited in any way in the present invention, and may be any rotation speed known to those skilled in the art.
After the deep polymerization reaction self-assembly is completed, the invention also preferably comprises the steps of filtering, washing and drying which are sequentially carried out; the filtration, washing and drying processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art. In a specific embodiment of the invention, the washing is specifically washing with deionized water for 3-6 times; the drying temperature is 70 ℃ specifically, and the drying time is 8h specifically.
In the present invention, the temperature of the second roasting is preferably 600 ℃ or less, more preferably 600 ℃; the time is preferably 4 h.
Obtaining Pt-Ru-CeO2-ZrO2After @ Co-Mn-HMS, the invention uses the Pt-Ru-CeO2-ZrO2Mixing the @ Co-Mn-HMS and water, and sequentially carrying out a second hydrothermal reaction and third roasting to obtain the high-temperature anoxic catalytic combustion catalyst.
In the present invention, the Pt-Ru-CeO2-ZrO2The mass ratio of @ Co-Mn-HMS to water is preferably 0.1-1: 1, more preferably 0.5: 1.
In the invention, the temperature of the second hydrothermal reaction is preferably 120-180 ℃, more preferably 140-160 ℃, and most preferably 150 ℃; the time is preferably 3 to 24 hours, more preferably 4 to 12 hours, and most preferably 6 hours.
After the second hydrothermal reaction is finished, the method also preferably comprises the steps of filtering, washing and drying which are sequentially carried out; the filtration, washing and drying processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art.
In the invention, the temperature of the third roasting is preferably 700-800 ℃, more preferably 710-740 ℃, and most preferably 720-730 ℃; the time is preferably 4 h.
The invention also provides the application of the high-temperature oxygen-deficient catalytic combustion catalyst in the technical scheme or the high-temperature oxygen-deficient catalytic combustion catalyst prepared by the preparation method in the technical scheme in catalyzing high-temperature combustion of liquid nitrogen-washed tail gas. The method of the present invention is not particularly limited, and may be carried out by a method known to those skilled in the art.
The high-temperature oxygen-deficient catalytic combustion catalyst provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
45.39gCe (NO)3)3·6H2O、62.70g Zr(NO3)4·5H2O、8.47g Y(NO3)3·6H2O、6.7gLa(NO3)3·6H2Mixing O and 454g of water to obtain a mixed metal salt solution, adding 86.57g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, carrying out heating homogeneous precipitation reaction at 95 ℃ for 5h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 700 ℃ for 2h to obtain 41.02g of a first carrier product;
after 41.02g of the first carrier product and 12.3g of water were mixed, 0.38g of RuCl was added3·6H2O, 28.71g citric acid, 0.37g H14Cl6O6Stirring Pt and 16.4g of ethyl acetate for 3 hours, adding 0.19g of hydrazine hydrate, and carrying out a reduction reaction, wherein the reduction reaction is carried out under the condition of stirring at room temperature, filtering, and mixing 41.3g of obtained solid with 27.53g of absolute ethyl alcohol to obtain 68.36g of a first dispersion product with the solid content of 60%;
heating 46.81g of dodecylamine to liquid (58.4mL) and 973.4mL of mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 5:1), mixing, stirring vigorously at room temperature for 3h, adding 68.36g of the first dispersion product, dropwise adding 156.0g of tetraethoxysilane, stirring continuously for 1h, and adding 24.3g of Co (NO) (NO: 1)3)2·6H2O and 11.4gMn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 800 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein CeO2、ZrO2The contents are 18% and Y2O3Content of La 2.5%2O32.5% of Pt, 0.18% of Ru, 0.1% of Co3O4Content of 7% MnO2Content 6.7% and HMS content 45%).
Example 2
52.96g of Ce (NO)3)3·6H2O、73.15g Zr(NO3)4·5H2O、13.56gY(NO3)3·6H2O、6.64g La(NO3)3·6H2Mixing O and 529.6g of water to obtain a mixed metal salt solution, adding 103.6g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, carrying out heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 800 ℃ for 2h to obtain 48.5g of a first carrier product;
will 4After 8.5g of the first carrier product and 14.55g of water were mixed, 0.77g of RuCl was added3·6H2O, 33.95g citric acid, 0.21g H14Cl6O6Stirring Pt and 19.4g of ethyl acetate for 3 hours, adding 0.37g of hydrazine hydrate, and carrying out a reduction reaction, wherein the reduction reaction is carried out under the condition of stirring at room temperature, filtering, and mixing 48.8g of obtained solid with 32.33g of absolute ethyl alcohol to obtain 80.83g of a first dispersion product with the solid content of 60%;
after 43.69g of dodecylamine was heated to a liquid (54.51mL), mixed with 908.5mL of a mixture of ethanol and deionized water, stirred vigorously at room temperature for 3 hours, then 80.83g of the first dispersion product was added and 145.6g of tetraethoxysilane was added dropwise, stirring continued for 1 hour, and 13.89g of Co (NO) (NO: W) was added3)2·6H2O and 8.85g Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 800 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein CeO2、ZrO2The contents are all 21% and Y2O3Content of La 4%2O32.5% of Pt, 0.1% of Ru, 0.2% of Co3O4Content of 4% MnO2Content 5.2% and HMS content 42%).
Example 3
55.48g Ce (NO)3)3·6H2O、76.63g Zr(NO3)4·5H2O、6.78g Y(NO3)3·6H2O、3.18g La(NO3)3·6H2Mixing O and 554.8g water to obtain mixed metal salt solution, adding 99.53g urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, heating at 90 deg.C for homogeneous precipitation reaction for 6h, performing hydrothermal reaction at 150 deg.C for 24h, filtering, washing with deionized water for 6 times, drying at 80 deg.C for 6h, and drying at 7Roasting at 40 ℃ for 2h to obtain 47.2g of a first carrier product;
after 47.2g of the first carrier product and 14.16g of water were mixed, 0.39g of RuCl was added3·6H2O、0.14H14Cl6O6Stirring Pt, 33.04g of citric acid and 18.88g of ethyl acetate for 3 hours, adding 0.34g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 47.37g of obtained solid with 31.46g of absolute ethyl alcohol to obtain 78.67g of a first dispersion product with the solid content of 60%;
41.61g of dodecylamine is heated into liquid (51.91mL) and mixed with 865.2mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1), the mixture is stirred vigorously for 3 hours at room temperature, then 78.67g of the first dispersion product is added, 138.7g of tetraethoxysilane is added dropwise, the stirring is continued for 1 hour, and 10.41g of Co (NO) (NO: 1) is added3)2·6H2O and 7.88g Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 800 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein CeO2、ZrO2The content is 22 percent and Y2O3Content of 2% La2O31.2% of Pt, 0.07% of Ru, 0.1% of Co3O4Content of 3% MnO2Content 4.63% and HMS content 45%).
Example 4
60.53g Ce (NO)3)3·6H2O、83.60g Zr(NO3)4·5H2O、10.17Y(NO3)3·6H2O、5.31g La(NO3)3·6H2Mixing O with 605.3g of water to obtain a mixed metal salt solution, adding 112g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, and fermenting at 90 deg.CCarrying out raw heating homogeneous precipitation reaction for 6h, carrying out hydrothermal reaction for 24h at 150 ℃, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 720 ℃ for 2h to obtain 53.0g of a first carrier product;
after mixing 53.0g of the first carrier product with 15.9g of water, 0.81g of RuCl was added3·6H2O、0.19g H14Cl6O6Stirring Pt, 37.1g of citric acid and 21.2g of ethyl acetate for 3 hours, adding 0.64g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 53.3g of obtained solid with 35.33g of absolute ethyl alcohol to obtain 88.33g of a first dispersion product with the solid content of 60%;
46.61g of dodecylamine is heated to be liquid (51.91mL) and mixed with 865.26mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1), the mixture is stirred vigorously for 3 hours at room temperature, 88.33g of the first dispersion product is added, 138.7g of tetraethoxysilane is added dropwise, the stirring is continued for 1 hour, and 10.41g of Co (NO) (NO: 1) is added3)2·6H2O and 6.30g Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 700 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein, CeO2、ZrO2The contents are all 24 percent and Y2O3All contents of 3% and La2O32% of Pt, 0.09% of Ru, 0.21% of Co3O4Content of 3% MnO2Content 3.7% HMS content 40%).
Example 5
65.57gCe (NO)3)3·6H2O、90.56g Zr(NO3)4·5H2O、3.39g Y(NO3)3·6H2O、1.32g La(NO3)3·6H2O and 655g of water to obtain a mixed metal saltAdding 112.3g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5) into the solution, stirring for 2h, carrying out heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 720 ℃ for 2h to obtain 53.5g of a first carrier product;
after 53.5g of the first carrier product and 16.05g of water were mixed, 0.39g of RuCl was added3·6H2O、0.42g H14Cl6O6Stirring Pt, 37.45g of citric acid and 21.4g of ethyl acetate for 3 hours, adding 0.50g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 53.8g of obtained solid with 35.67g of absolute ethyl alcohol to obtain 89.17g of a first dispersion product with the solid content of 60%;
41.61g of dodecylamine is heated into liquid (51.92mL) and mixed with 865.26mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1), the mixture is stirred vigorously for 3 hours at room temperature, 89.17g of the first dispersion product is added, 138.7g of ethyl orthosilicate is added dropwise, the stirring is continued for 1 hour, and 11.11g of Co (NO) (NO: 1) is added3)2·6H2O and 5.11g Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 100g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 700 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein, CeO2、ZrO2All contents are 26%, Y2O3Is 1% of La2O30.5% of Pt, 0.2% of Ru, 0.1% of Co3O4Content of 3.2% MnO2Content 3% HMS content 40%).
Example 6
68.10Ce (NO)3)3·6H2O、94.05g Zr(NO3)4·5H2O、2.37g Y(NO3)3·6H2O、1.86g La(NO3)3·6H2Mixing O and 681g of water to obtain a mixed metal salt solution, adding 116.1g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, carrying out heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 700 for 2h to obtain 55.4g of a first carrier product;
after mixing 55.4g of the first carrier product with 16.62g of water, 0.42g of RuCl was added3·6H2O、0.18g H14Cl6O6Stirring Pt, 38.78g of citric acid and 22.16g of ethyl acetate for 3 hours, adding 0.38g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 55.6g of obtained solid with 36.93g of absolute ethyl alcohol to obtain 92.33g of a first dispersion product with the solid content of 40%;
41.61g of dodecylamine is heated to be liquid (51.91mL) and mixed with 815.26mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1), the mixture is stirred vigorously for 3 hours at room temperature, 92.33g of first dispersion product is added, 138.7g of ethyl orthosilicate is added dropwise, the stirring is continued for 1 hour, and 10.41g of Co (NO) (NO is added)3)2·6H2O and 2.38g Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@Co-Mn-HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ Co-Mn-HMS with 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 800 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein CeO2、ZrO2The contents are all 27% and Y2O30.7% of La2O30.7% of Pt, 0.09% of Ru, 0.11% of Co3O4Content of 3% MnO2Content 1.4% HMS content 40%).
Example 7
70.62g Ce (NO)3)3·6H2O、97.53g Zr(NO3)4·5H2O、5.08g Y(NO3)3·6H2O、3.99g La(NO3)3·6H2Mixing O and 706g of water to obtain a mixed metal salt solution, adding 123.84g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, carrying out heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 800 ℃ for 2h to obtain 59g of a first carrier product;
after 59g of the first carrier product and 17.7g of water were mixed, 0.39g of RuCl was added3·6H2O、0.21g H14Cl6O6Stirring Pt, 23.6g of ethyl acetate and 41.3g of citric acid for 3 hours, adding 0.38g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 59.2g of obtained solid with 39.33g of absolute ethyl alcohol to obtain 98.33g of a first dispersion product with the solid content of 60%;
heating 36.4g of dodecylamine to liquid (45.4mL) and 121.36mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1), mixing, stirring vigorously at room temperature for 3 hours, adding 98.33g of the first dispersion product, adding 121.36g of ethyl orthosilicate dropwise, stirring continuously for 1 hour, adding 9.7g of Co (NO) (NO: 1)3)2·6H2O and 5.11gMn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@HMS;
100g of the Pt-Ru-CeO2-ZrO2Mixing @ HMS with 200g of water, carrying out hydrothermal reaction at 150 ℃ for 6h, filtering, washing and drying, and roasting at 800 ℃ for 4h to obtain the high-temperature anoxic catalytic combustion catalyst (wherein, CeO2、ZrO2The contents of Y and Y are both 28%2O3、La2O31.5% of Pt, 0.1% of Ru, and Co3O4Content of 2.8%, MnO2Content 3% and HMS content 35%).
Example 8
75.66g of Ce (NO)3)3·6H2O、104.50g Zr(NO3)4·5H2O、10.17g Y(NO3)3·6H2O、4.25g La(NO3)3·6H2Mixing O and 756g of water to obtain a mixed metal salt solution, adding 136.38g of urea (the molar ratio of the total molar ratio of Ce, Zr, Y and La ions to the urea is 1: 5), stirring for 2h, carrying out heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out hydrothermal reaction at 150 ℃ for 24h, filtering, washing with deionized water for 6 times, drying at 80 ℃ for 6h, and roasting at 740 ℃ for 2h to obtain 64.5g of a first carrier product;
after mixing 64.5g of the first carrier product with 19.35g of water, 1.16g of RuCl was added3·6H2O、0.21g H14Cl6O6Stirring Pt, 45.22g of citric acid and 25.8g of ethyl acetate for 3 hours, adding 0.87g of hydrazine hydrate, carrying out reduction reaction under the condition of stirring at room temperature, filtering, and mixing 65g of obtained solid with 43.06g of absolute ethyl alcohol to obtain 107.66g of a first dispersion product with the solid content of 40%;
heating 36.41g of dodecylamine to liquid (45.42mL), mixing with 757.1mL of mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 5:1), stirring vigorously for 3h at room temperature, adding 107.66g of the first dispersion product, dropwise adding 121.36g of ethyl orthosilicate, and stirring continuously for 1h without adding Co (NO)3)2·6H2O and Mn (NO)3)2Stirring at room temperature for 20h, filtering, washing with deionized water for 6 times, drying at 70 deg.C for 8h, and calcining at 600 deg.C for 4h to obtain 100g of Pt-Ru-CeO2-ZrO2@HMS;
Subjecting the Pt-Ru-CeO2-ZrO2Mixing the @ HMS with the first dispersion product and 200g of water, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, washing and drying, and roasting for 4h at 800 ℃ to obtain the high-temperature oxygen-deficient catalytic combustion catalyst (wherein, CeO2、ZrO2The contents are all 30 percent and Y2O3Content of La 3%2O3The content is 1.5%, Pt content0.2%, Ru content 0.3%, Co3O4Content of 0% MnO2Content 0% and HMS content 35%).
Test example
The high-temperature oxygen-deficient catalytic combustion catalyst prepared in the embodiment 1-8 is subjected to a high-temperature oxygen-deficient catalytic performance test, and the specific test process is as follows: the catalysts prepared in the above examples 1 to 8 were bound by an adhesive and then formed into spherical pellets by ball-turning, and the spherical catalysts having a pellet size of 2 to 3mm were placed in a fixed bed quartz reactor having an inner diameter of 12 mm. The raw material gas is: 11.5% CO, 1.8% H2、1.2%CH4Controlling the content of the nitrogen to be 0.2 percent, and taking the nitrogen as balance gas; setting the reaction space velocity at 2000h-1And (3) under normal pressure, wherein the test temperature is 600 ℃ at the beginning of the reaction, and the catalytic combustion reaction temperature of the liquid nitrogen-washed tail gas is 650-850 ℃ after the ignition temperature is obtained. The evaluation results of the above catalysts are shown in Table 1, and the evaluation indexes are CO residue and CH in combustible components4And (4) residual quantity.
TABLE 1 Performance results for catalysts prepared in examples 1-8
As shown in Table 1, the high temperature oxygen-deficient catalytic combustion catalyst of the present invention has a good catalytic efficiency under high temperature oxygen-deficient conditions.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.