CN113457721B - High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof - Google Patents
High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of tail gas catalytic oxidation, in particular to a high-temperature anoxic catalytic combustion catalyst, and a preparation method and application thereof. 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 CeO 2 ‑ZrO 2 @ HMS; the CeO 2 ‑ZrO 2 @ CeO in HMS 2 ‑ZrO 2 Doped with yttrium oxide and lanthanum oxide; the noble metal active component is Ru and Pt. The high-temperature oxygen-deficient catalytic combustion catalyst has better catalytic efficiency and carbon deposition resistance under the high-temperature oxygen-deficient condition.
Description
Technical Field
The invention relates to the technical field of tail gas catalytic oxidation, in particular to a high-temperature anoxic catalytic combustion catalyst, and a preparation method and application thereof.
Background
The liquid nitrogen washing tail gas contains 5-10% of CO H 2 (1～4％)、CH 4 (1-1.5%), ar and N 2 The heat value of the equal gas is about 1200-2100 kJ/m 3 . The liquid nitrogen wash tail gas contains no oxygen, and although the content of CO is high, the liquid nitrogen wash tail gas is difficult to directly combust even if air is supplemented. The liquid nitrogen washing tail gas is not allowed to be directly discharged, and in order to meet the requirement of environmental protection, some enterprises adopt a method of adding synthesis gas to increase combustible gas components in the liquid nitrogen washing tail gas and then lighting a 'ceiling lamp' for combustion, so that resources are wasted, a large amount of greenhouse gas is discharged, and a serious atmosphere pollution is caused due to incomplete combustion of CO. Therefore, the liquid nitrogen tail gas washing catalyst with lower cost and wider application range is beneficial to saving a large amount of energy and can also greatly protect the environment.
At present, most of active components of the existing liquid nitrogen tail gas washing catalyst are palladium, but the palladium is a noble metal, the market price is about 600 yuan per gram, the cost for preparing the catalyst by using the palladium as the active component is too high, and in addition, when the concentration of CO in the liquid nitrogen tail gas washing is slightly higher than 9%, the existing liquid nitrogen tail gas washing low-temperature oxygen-deficient catalyst only adapts to the low temperature below 500 ℃, has higher heat value under the high-temperature condition and is easy to sinter; the existing high-temperature peroxide catalyst can adapt to the high temperature of over 800 ℃, but is not suitable for the oxygen-deficient environment, and the high-temperature oxygen-deficient environment is very easy to cause CH 4 The carbon deposition and the inactivation of the catalyst are caused by cracking and CO disproportionation reaction, and the sintering and the inactivation of the catalyst are easily caused by high temperature.
Disclosure of Invention
The invention aims to provide a high-temperature oxygen-deficient catalytic combustion catalyst, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
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 CeO 2 -ZrO 2 @ HMS; the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Doped with yttrium oxide and lanthanum oxide;
the noble metal active component is Ru and Pt.
Preferably, the catalyst also comprises a cocatalyst, and the cocatalyst is loaded in the carrier with the mesoporous structure.
Preferably, the promoter is an Mn oxide and/or a Co oxide.
Preferably, the high temperature anoxic catalytic combustion catalyst as set forth in claim 1 wherein the CeO 2 -ZrO 2 @ CeO in HMS 2 And ZrO 2 The total mass of the catalyst is 36 to 60 percent of the mass percentage of the high-temperature oxygen-deficient catalytic combustion catalyst;
the CeO 2 And ZrO 2 The mass ratio of (18-30): (18 to 30);
the CeO 2 -ZrO 2 The mass percentage of the HMS in the @ HMS in the high-temperature oxygen-deficient catalytic combustion catalyst is 30-45%.
Preferably, the mass percentage content of the yttrium oxide in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.5-5%;
the mass percentage of the lanthanum oxide in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.5-5%.
Preferably, the mass percentage content of the cocatalyst in the high-temperature oxygen-deficient catalytic combustion catalyst is 8-14%;
the mass percentage content of Pt in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.05-0.3%;
the mass percentage content of Ru in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.1-0.8%.
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-CeO 2 -ZrO 2 @ 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-CeO 2 -ZrO 2 Mixing 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.
Preferably, the temperature of the heating homogeneous precipitation reaction is 90-95 ℃, and the time is 2-5 h;
the temperature of the first hydrothermal reaction is 120-150 ℃, and the time is 12-24 h;
the temperature of the first roasting is 680-800 ℃, and the time is 2 hours;
preferably, the temperature of the second roasting is less than or equal to 600 ℃, and the time is 4 hours;
the temperature of the third roasting is 700-800 ℃, and the time is 4h.
The invention also provides the application of the high-temperature oxygen-deficient catalytic combustion catalyst in the technical scheme or the application of 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 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(ii) a The carrier with the mesoporous structure is CeO 2 -ZrO 2 @ HMS; the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Doped with yttrium oxide and lanthanum oxide; the noble metal active component is Ru and P.
Compared with the prior art, the invention has the following excellent effects:
1) The high-temperature oxygen-deficient catalytic combustion catalyst can be used for high-temperature oxygen-deficient combustion with the mass content of carbon monoxide in liquid nitrogen washing tail gas slightly higher than 9%, so that the problem that a low-temperature oxygen-deficient catalyst in the prior art is easy to sinter under a high-temperature condition is avoided, and the problem that the existing high-temperature catalyst is not suitable for an oxygen-deficient environment is also solved; the highest catalytic temperature of the high-temperature oxygen-deficient catalytic combustion catalyst is 700 ℃;
2) The high-temperature oxygen-deficient catalytic combustion catalyst contains HMS component, and can disperse CeO in the catalyst 2 -ZrO 2 The components avoid the problem of sintering in a high-temperature environment, provide a higher specific surface area, provide more active sites, facilitate the occurrence of catalytic reaction and improve the activity of the catalyst;
3) The noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is Ru and/or Pt, the market price of the noble metal active component is only 50% and 10% of the market price of palladium, the preparation cost of the high-temperature oxygen-deficient catalytic combustion catalyst is 40% -60% of that of the existing palladium catalyst, the production cost of the catalyst is greatly reduced, and the application of the high-temperature oxygen-deficient catalytic combustion catalyst in industrial production is facilitated;
4) In the high-temperature oxygen-deficient catalytic combustion catalyst, ceO is added 2 -ZrO 2 Yttrium oxide and lanthanum oxide are doped in the alloy, so that crystal lattices can be stabilized, and the high-temperature stability of the alloy is improved.
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 above-mentionedThe carrier with the mesoporous structure is CeO 2 -ZrO 2 @ HMS; the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Doped with yttrium oxide and lanthanum oxide;
the noble metal active component is Ru and Pt.
In the present invention, the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Dispersed in the mesoporous structure of HMS; the noble metal active component and the cocatalyst are loaded on the CeO 2 -ZrO 2 Of (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 CeO 2 -ZrO 2 @ HMS; the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Doped with yttrium oxide and lanthanum oxide. In the invention, the HMS is preferably a hexagonal mesoporous silica molecular sieve; the CeO 2 -ZrO 2 Preferably CeO 2 And ZrO 2 The solid solution composite of (1).
In the present invention, ceO 2 -ZrO 2 @ CeO in HMS 2 And ZrO 2 The mass percentage content of the total mass of the catalyst in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 36-60%, more preferably 43.7-51.3%, even more preferably 45-49.6%, and most preferably 46.5-47.2%; the CeO 2 And ZrO 2 The mass ratio of (2) is preferably (18 to 30): (18 to 30), more preferably (21.9 to 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 most preferably 2.0-3.0%; the lanthanum oxide is preferably lanthanum trioxide.
In the present invention, the CeO 2 -ZrO 2 The 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 oxygen-deficient 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 promoter in the high-temperature oxygen-deficient catalytic combustion catalyst is preferably 8-14%, and more preferably 10-12%. In a specific embodiment of the invention, the mass ratio of the Mn oxide to the Co oxide is specifically 7.5,5.5,6.
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 precious 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 to perform a reduction reaction to obtain a first dispersion product; the soluble precious 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-CeO 2 -ZrO 2 @ Co-Mn-HMS; the soluble salt corresponding to the cocatalyst comprises a soluble manganese salt and/or a soluble cobalt salt;
subjecting the Pt to-Ru-CeO 2 -ZrO 2 Mixing the @ Co-Mn-HMS with 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 then carrying out first roasting on an 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 sequentially specific to cerium nitrate, zirconium nitrate, yttrium nitrate and lanthanum nitrate.
In the present 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 to 0.15), more preferably (1.2 to 1.8): (1.2-1.8): (0.04-0.09): (0.04 to 0.09), most preferably (1.4 to 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 CeO 2 -ZrO 2 And further is beneficial to controlling the formation of the CeO with uniform size 2 -ZrO 2 The 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, 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 present invention, the temperature of the first hydrothermal reaction is preferably 120 to 150 ℃, more preferably 130 to 140 ℃; the time is preferably 12 to 24 hours, 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 present invention, the washing is preferably performed 3 to 6 times with deionized water; the drying is drying at 80 ℃ for 6h.
In the present invention, the temperature of the first roasting is preferably 680 to 800 ℃, more preferably 690 to 740 ℃, and most preferably 700 to 730 ℃; the time is 2h.
In the present invention, the first carrier product is specifically CeO doped with yttrium oxide and lanthanum oxide 2 -ZrO 2 。
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 particular embodiment of the invention, the soluble ruthenium salt is in particular ruthenium chloride; the soluble platinum salt is specifically H 14 Cl 6 O 6 Pt。
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 to 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 noble metal salt is soluble ruthenium salt and soluble platinum salt, the mass ratio of the ruthenium metal simple substance in the soluble ruthenium salt to the platinum metal simple substance in the soluble platinum salt is preferably (0.05-0.4): (0.05 to 0.3), more preferably (0.08 to 0.21): (0.08 to 0.21), most preferably (0.13 to 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, and the rotating speed is preferably 500-1000 rpm/min, more preferably 600-800 rpm/min; the time is preferably 10 to 30min, more preferably 15 to 25min, and most preferably 18 to 22min. 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 present invention, the temperature of the reduction reaction is preferably room temperature, and the time is preferably 15 to 30min.
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%, 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-CeO 2 -ZrO 2 。
After the first dispersion product is obtained, the invention mixes the dodecylamine, the first dispersion product, the solvent and the ethyl orthosilicate, after the polymerization reaction self-assembly, adds the soluble salt corresponding to the cocatalyst, and sequentially carries out the deep polymerization reaction self-assembly and the second roasting to obtain the Pt-Ru-CeO 2 -ZrO 2 @ 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 to 8:1, more preferably 5:1.
In the present invention, the mass ratio of dodecylamine to tetraethoxysilane is preferably (1 to 5): (2 to 8), more preferably (2 to 3): (5-6). In the present invention, the volume ratio of the dodecylamine to the solvent is preferably (5 to 30): 500, more preferably (6 to 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 present invention, the mass ratio of the first dispersion product, the ethyl orthosilicate, and the soluble salt corresponding to the co-catalyst is preferably (36.15-61.5): (105 to 158): (8 to 20), more preferably (40 to 58): (125-150): (9 to 13), most preferably (45 to 52): (133 to 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 1h. 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 salts corresponding to the cocatalyst are soluble manganese salts and soluble cobalt salts, the molar ratio of the soluble manganese salts to the soluble cobalt salts is preferably (1-4) to (1-4), more preferably (2-3) to (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 present invention, the temperature of the deep polymerization self-assembly is preferably room temperature, and the time is preferably 10 to 30 hours, more preferably 15 to 25 hours, and most preferably 20 hours. 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 to 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 4h.
Obtaining Pt-Ru-CeO 2 -ZrO 2 After @ Co-Mn-HMS, the invention uses the Pt-Ru-CeO 2 -ZrO 2 Mixing 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-CeO 2 -ZrO 2 The mass ratio of @ Co-Mn-HMS to water is preferably 0.1 to 1:1, more preferably 0.5.
In the present invention, the temperature of the second hydrothermal reaction is preferably 120 to 180 ℃, more preferably 140 to 160 ℃, and most preferably 150 ℃; the time is preferably 3 to 24 hours, more preferably 4 to 12 hours, 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 present invention, the temperature of the third roasting is preferably 700 to 800 ℃, more preferably 710 to 740 ℃, and most preferably 720 to 730 ℃; the time is preferably 4h.
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 ·6H 2 O、62.70g Zr(NO 3 ) 4 ·5H 2 O、8.47g Y(NO 3 ) 3 ·6H 2 O、6.7gLa(NO 3 ) 3 ·6H 2 Mixing 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 added 3 ·6H 2 O, 28.71g citric acid, 0.37g H 14 Cl 6 O 6 Pt and 16.4g of ethyl acetate are stirred for 3 hours, 0.19g of hydrazine hydrate is added, and reduction reaction occursThe reduction reaction was carried out under conditions of stirring at room temperature, filtration, and mixing 41.3g of the obtained solid with 27.53g of absolute ethanol to obtain 68.36g of a first dispersion product having a solid content of 60%;
46.81g of dodecylamine is heated to be liquid (58.4 mL) and 973.4mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the deionized water is 5:1) are mixed, stirred vigorously at room temperature for 3h, 68.36g of the first dispersion product is added, 156.0g of tetraethoxysilane is added dropwise, stirring is continued for 1h, and 24.3g of Co (NO) (NO: 3242) is added 3 ) 2 ·6H 2 O and 11.4gMn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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 CeO 2 、ZrO 2 The contents are 18% and Y 2 O 3 Content of La 2.5% 2 O 3 2.5% of Pt, 0.18% of Ru, 0.1% of Co 3 O 4 Content of 7% MnO 2 Content 6.7% and HMS content 45%).
Example 2
52.96g of Ce (NO) 3 ) 3 ·6H 2 O、73.15g Zr(NO 3 ) 4 ·5H 2 O、13.56gY(NO 3 ) 3 ·6H 2 O、6.64g La(NO 3 ) 3 ·6H 2 Mixing 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 a heating homogeneous precipitation reaction at 90 ℃ for 6h, carrying out a 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;
after 48.5g of the first carrier product and 14.55g of water were mixed, 0.77g of RuCl was added 3 ·6H 2 O, 33.95g lemonAcid, 0.21g H 14 Cl 6 O 6 Stirring Pt and 19.4g of ethyl acetate for 3 hours, adding 0.37g of hydrazine hydrate, and carrying out reduction reaction, wherein the reduction reaction condition is 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 60% of solid content;
after 43.69g of dodecylamine was heated to a liquid (54.51 mL) and mixed with 908.5mL of ethanol and deionized water, vigorously stirred at room temperature for 3 hours, 80.83g of the first dispersion product was added and 145.6g of ethyl orthosilicate was added dropwise, stirring was continued for 1 hour, and 13.89g of Co (NO) (NO: 1 g) was added 3 ) 2 ·6H 2 O and 8.85g Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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 CeO 2 、ZrO 2 The contents are all 21% and Y 2 O 3 Content of La 4% 2 O 3 2.5% of Pt, 0.1% of Ru, 0.2% of Co 3 O 4 Content of 4% MnO 2 Content 5.2% and HMS content 42%).
Example 3
55.48g Ce (NO) 3 ) 3 ·6H 2 O、76.63g Zr(NO 3 ) 4 ·5H 2 O、6.78g Y(NO 3 ) 3 ·6H 2 O、3.18g La(NO 3 ) 3 ·6H 2 Mixing O and 554.8g of water to obtain a mixed metal salt solution, adding 99.53g 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 47.2g of a first carrier product;
producing 47.2g of the first vectorThe mixture was mixed with 14.16g of water, and 0.39g of RuCl was added 3 ·6H 2 O、0.14H 14 Cl 6 O 6 Stirring 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 first dispersion product with the solid content of 60%;
41.61g dodecylamine is heated to liquid (51.91 mL) and 865.2mL mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 5:1) are mixed, stirred vigorously at room temperature for 3h, 78.67g first dispersion product is added and 138.7g ethyl orthosilicate is added dropwise, stirring is continued for 1h, and 10.41g Co (NO) (NO: 10.41 g) 3 ) 2 ·6H 2 O and 7.88g Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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 CeO 2 、ZrO 2 The content is 22 percent and Y 2 O 3 Content of 2% La 2 O 3 1.2% of Pt, 0.07% of Ru, 0.1% of Co 3 O 4 Content of 3% MnO 2 Content 4.63% and HMS content 45%).
Example 4
60.53g Ce (NO) 3 ) 3 ·6H 2 O、83.60g Zr(NO 3 ) 4 ·5H 2 O、10.17Y(NO 3 ) 3 ·6H 2 O、5.31g La(NO 3 ) 3 ·6H 2 Mixing O and 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, 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, and drying at 80 DEG CAfter drying for 6h, 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 added 3 ·6H 2 O、0.19g H 14 Cl 6 O 6 Stirring 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 dodecylamine is heated to liquid (51.91 mL) and 865.26mL mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 5:1) are mixed, stirred vigorously at room temperature for 3h, then 88.33g of the first dispersion product is added and 138.7g of ethyl orthosilicate is added dropwise, stirring is continued for 1h, and 10.41g of Co (NO) (NO: 10.41 g) 3 ) 2 ·6H 2 O and 6.30g Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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, ceO 2 、ZrO 2 The contents are both 24% and Y 2 O 3 All contents of 3% and La 2 O 3 2% of Pt, 0.09% of Ru, 0.21% of Co 3 O 4 Content of 3% MnO 2 Content 3.7% HMS content 40%).
Example 5
65.57gCe (NO) 3 ) 3 ·6H 2 O、90.56g Zr(NO 3 ) 4 ·5H 2 O、3.39g Y(NO 3 ) 3 ·6H 2 O、1.32g La(NO 3 ) 3 ·6H 2 Mixing O and 655g of water to obtain a mixed metal salt solution, adding 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), stirring for 2h,heating at 90 ℃ for homogeneous precipitation reaction 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;
53.5g of the first support product are mixed with 16.05g of water, 0.39g of RuCl are added 3 ·6H 2 O、0.42g H 14 Cl 6 O 6 Stirring 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 laurylamine was heated to a liquid (51.92 mL) and 865.26mL mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water was 5:1), stirred vigorously at room temperature for 3h, then 89.17g of the first dispersion was added dropwise to 138.7g tetraethoxysilane, stirring was continued for 1h, and 11.11g Co (NO: 11g 3 ) 2 ·6H 2 O and 5.11g Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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, ceO 2 、ZrO 2 All contents are 26%, Y 2 O 3 Is 1% of La 2 O 3 0.5% of Pt, 0.2% of Ru, 0.1% of Co 3 O 4 Content of 3.2% MnO 2 Content 3% HMS content 40%).
Example 6
68.10Ce (NO) 3 ) 3 ·6H 2 O、94.05g Zr(NO 3 ) 4 ·5H 2 O、2.37g Y(NO 3 ) 3 ·6H 2 O、1.86g La(NO 3 ) 3 ·6H 2 O and 681g of water to obtain mixed goldAfter the carrier belongs to a salt solution, 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) is added, the mixture is stirred for 2 hours, after heating homogeneous precipitation reaction is carried out for 6 hours at 90 ℃, hydrothermal reaction is carried out for 24 hours at 150 ℃, the mixture is filtered, washed for 6 times by deionized water, dried for 6 hours at 80 ℃, and roasted for 2 hours at 700 ℃ 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 added 3 ·6H 2 O、0.18g H 14 Cl 6 O 6 Stirring 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 dodecylamine is heated to liquid (51.91 mL) and 815.26mL mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water is 5:1) are mixed, stirred vigorously at room temperature for 3h, then 92.33g of the first dispersion product is added and 138.7g of ethyl orthosilicate is added dropwise, stirring is continued for 1h, and 10.41g of Co (NO) (NO: 10.41 g) 3 ) 2 ·6H 2 O and 2.38g Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @Co-Mn-HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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 CeO 2 、ZrO 2 The contents are all 27% and Y 2 O 3 0.7% of La 2 O 3 0.7% of Pt, 0.09% of Ru, 0.11% of Co 3 O 4 Content of 3% MnO 2 Content 1.4% HMS content 40%).
Example 7
70.62g Ce (NO) 3 ) 3 ·6H 2 O、97.53g Zr(NO 3 ) 4 ·5H 2 O、5.08g Y(NO 3 ) 3 ·6H 2 O、3.99g La(NO 3 ) 3 ·6H 2 Mixing 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 added 3 ·6H 2 O、0.21g H 14 Cl 6 O 6 Stirring 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 (45.4 mL) and 121.36mL of a 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 3h, adding 98.33g of the first dispersion product, dropwise adding 121.36g of ethyl orthosilicate, stirring continuously for 1h, and adding 9.7g of Co (NO) (NO: 9.7 g) 3 ) 2 ·6H 2 O and 5.11gMn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @HMS；
100g of the Pt-Ru-CeO 2 -ZrO 2 Mixing @ 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 anoxic catalytic combustion catalyst (wherein CeO) 2 、ZrO 2 The contents of Y and Y are both 28% 2 O 3 、La 2 O 3 1.5% of Pt, 0.1% of Ru, and Co 3 O 4 Content of 2.8%, mnO 2 Content 3% and HMS content 35%).
Example 8
75.66g of Ce (NO) 3 ) 3 ·6H 2 O、104.50g Zr(NO 3 ) 4 ·5H 2 O、10.17g Y(NO 3 ) 3 ·6H 2 O、4.25g La(NO 3 ) 3 ·6H 2 Mixing 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 added 3 ·6H 2 O、0.21g H 14 Cl 6 O 6 Pt, 45.22g of citric acid and 25.8g of ethyl acetate are stirred for 3 hours, 0.87g of hydrazine hydrate is added for reduction reaction, the reduction reaction is carried out under the condition of stirring at room temperature, filtration is carried out, 65g of obtained solid is mixed with 43.06g of absolute ethyl alcohol, and 107.66g of first dispersion product with the solid content of 40% is obtained;
heating 36.41g of dodecylamine to liquid (45.42 mL) and 757.1mL 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 107.66g of first dispersion product, dropwise adding 121.36g of ethyl orthosilicate, and stirring continuously for 1h without adding Co (NO) (NO: 121.36g of ethyl orthosilicate) 3 ) 2 ·6H 2 O and Mn (NO) 3 ) 2 Stirring 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-CeO 2 -ZrO 2 @HMS；
Subjecting the Pt-Ru-CeO 2 -ZrO 2 Mixing 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, ceO 2 、ZrO 2 The contents are all 30 percent and Y 2 O 3 Content of La 3% 2 O 3 1.5% of Pt, 0.2% of Ru, 0.3% of Co 3 O 4 Content of 0% MnO 2 Content of 0% and HMS content35% for the case).
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 obtained in examples 1 to 8 were bound with a binder and then pelletized to form spherical catalysts having a pellet size of 2 to 3mm, and the spherical catalysts were charged into a fixed bed quartz reactor having an inner diameter of 12 mm. The raw material gas is: 11.5% CO, 1.8% H 2 、1.2％CH 4 Controlling the content of the nitrogen to be 0.2 percent, and taking the nitrogen as balance gas; setting the reaction space velocity at 2000h -1 Normal pressure, the testing 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 components 4 And (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 invention has better catalytic efficiency under the condition of high temperature oxygen deficiency.
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.
Claims (10)
1. The high-temperature oxygen-deficient catalytic combustion catalyst is characterized by comprising 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 CeO 2 -ZrO 2 @ HMS; the CeO 2 -ZrO 2 @ CeO in HMS 2 -ZrO 2 Doped with yttrium oxide and lanthanum oxide;
the noble metal active component is Ru and Pt.
2. The high temperature oxygen deficient catalytic combustion catalyst according to claim 1 further comprising a promoter supported on said support having a mesoporous structure.
3. A high temperature oxygen deficient catalytic combustion catalyst as claimed in claim 2 wherein the promoter is an oxide of Mn and/or Co.
4. The high temperature oxygen deficient catalytic combustion catalyst of claim 1 wherein the CeO is 2 -ZrO 2 @ CeO in HMS 2 And ZrO 2 The total mass percentage of the catalyst in the high-temperature oxygen-deficient catalytic combustion catalyst is 36-60 percent;
the CeO 2 And ZrO 2 The mass ratio of (18-30): (18 to 30);
the CeO 2 -ZrO 2 The mass percentage of the HMS in the @ HMS in the high-temperature oxygen-deficient catalytic combustion catalyst is 30-45%.
5. The high temperature oxygen deficient catalytic combustion catalyst of claim 1 wherein the yttrium oxide is present in the high temperature oxygen deficient catalytic combustion catalyst in an amount of from 0.5% to 5% by weight;
the mass percentage of the lanthanum oxide in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.5-5%.
6. The high-temperature oxygen-deficient catalytic combustion catalyst according to claim 2, wherein the mass percentage of the promoter in the high-temperature oxygen-deficient catalytic combustion catalyst is 8 to 14%;
the mass percentage content of Pt in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.05-0.3%;
the mass percentage content of Ru in the noble metal active component in the high-temperature oxygen-deficient catalytic combustion catalyst is 0.1-0.8%.
7. The process for preparing a high temperature oxygen deficient catalytic combustion catalyst as claimed in any one of claims 1 to 6 comprising 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;
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 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-CeO 2 -ZrO 2 @ 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-CeO 2 -ZrO 2 Mixing 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.
8. The preparation method according to claim 7, wherein the temperature of the heating homogeneous precipitation reaction is 90-95 ℃ and the time is 2-5 h;
the temperature of the first hydrothermal reaction is 120-150 ℃ and the time is 12-24 h;
the temperature of the first roasting is 680-800 ℃, and the time is 2h.
9. The preparation method of claim 7, wherein the temperature of the second roasting is less than or equal to 600 ℃ and the time is 4 hours;
the temperature of the third roasting is 700-800 ℃, and the time is 4h.
10. Use of the high-temperature oxygen-deficient catalytic combustion catalyst according to any one of claims 1 to 6 or the high-temperature oxygen-deficient catalytic combustion catalyst prepared by the preparation method according to any one of claims 7 to 9 in catalyzing high-temperature combustion of liquid nitrogen-washed tail gas.
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Inventor after: Zhang Qiulin Inventor after: Cui Sihan Inventor after: Chen Jianjun Inventor after: Lv Dongli Inventor after: Zhang Pengyu Inventor after: Liu Juanyu Inventor before: Cui Sihan Inventor before: Zhang Qiulin Inventor before: Chen Jianjun Inventor before: Lv Dongli Inventor before: Zhang Pengyu Inventor before: Liu Juanyu |