CN114917924B - Catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene, and preparation method and application thereof - Google Patents

Catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene, and preparation method and application thereof Download PDF

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CN114917924B
CN114917924B CN202110769813.7A CN202110769813A CN114917924B CN 114917924 B CN114917924 B CN 114917924B CN 202110769813 A CN202110769813 A CN 202110769813A CN 114917924 B CN114917924 B CN 114917924B
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黄家辉
张军营
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a preparation method and application of a catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene. The catalyst comprises an active component and a carrier; the active component comprises an active element; the active element is Au; the carrier is a composite metal oxide carrier; the metal element in the composite metal oxide comprises Mo, bi, fe, co, ce, X element; and X is at least one selected from K, rb, cs, ni, cu. Gold and oxide support are produced by co-deposition. The catalyst is applied to the reaction of preparing the methacrolein by the selective oxidation of the tertiary butanol (isobutene), can realize the efficient conversion of the tertiary butanol (isobutene) to the methacrolein at a relatively low temperature, has the highest conversion rate and the highest selectivity of 93 percent and 95 percent respectively, and has very wide industrial application prospect.

Description

Catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene, and preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene, and a preparation method and application thereof, belonging to the field of catalyst preparation and application.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material due to good physical and chemical properties, can be directly applied as an organic chemical product, and is widely applied to various industries such as organic glass (PMMA), paint, leather, methacrylic acid higher esters and the like, so that the market prospect is very wide. The traditional technology for producing MMA in industry is mainly acetone cyanohydrin method (ACH method), because acetone and highly toxic hydrocyanic acid are used as raw materials, and highly corrosive sulfuric acid is needed in the reaction process, the technology has serious environmental pollution and low atom utilization rate.
In recent years, MMA prepared from isobutene (tertiary butanol) is widely focused, and has a high atomic utilization rate, a simple and green process and a good industrial application prospect.
The method for converting isobutene into MMA by adopting the isobutene oxidation method is a comprehensive utilization process route of C4 hydrocarbon with low cost, little pollution and good economic benefit. At present, three main technological routes for preparing MMA by isobutene oxidation are provided: 1) Isobutene is first oxidized to Methacrolein (MAL), then further oxidized to methacrylic acid (MAA), and finally MMA is produced by an esterification process. This route has been industrialized and is becoming mature. The China academy of sciences process engineering institute, shanghai Hua Yi (group) company and China petrochemical Shanghai chemical industry institute have deeper researches on the catalyst and the process. But the MMA product can be obtained through three steps of reactions in the process route, so that the process flow is longer and the product yield is lower. 2) The isobutene is directly oxidized to acrylic acid and then transesterified to MMA. The process is simplified and the cost is reduced compared with the first one. But the industrial process has not been achieved yet. 3) Isobutene is first oxidized into methacrolein, and then oxidized with methanol to produce MMA. The process has the advantages of short synthetic route, high atomic utilization rate and the like, and has a relatively high industrial application prospect. However, the method is industrially applied only by the Asahi chemical company in Japan, and no industrial application is advanced in China. Therefore, the technology for preparing methyl methacrylate by isobutene with domestic independent intellectual property has important significance for breaking through the monopoly of foreign technology and improving the technical level of the related field in China. Meanwhile, the process is simple, green and less in pollution, and has good environmental benefit and relatively high economic benefit.
The key point of the process for preparing methyl methacrylate from isobutene through methacrolein is the research and development of a catalyst related to the preparation of methyl methacrylate by the selective oxidation of isobutene to prepare methacrolein and the oxidative esterification of methacrolein. At present, the research on the catalyst for preparing methyl methacrylate by oxidizing and esterifying the methyl acraldehyde by the research group has made breakthrough progress, and the catalyst has excellent catalyst stability and good catalytic performance in the oxidizing and esterifying reaction process of the methyl acraldehyde, and a series of indexes such as reactant conversion rate, product selectivity and the like reach or even exceed the level of foreign catalysts.
The most widely used catalyst for the reaction of preparing methacrolein by the selective oxidation of isobutene is Mo-Bi series composite oxide catalyst at present. The catalyst has very good catalytic activity (about 98%) in the oxidation of isobutene (tertiary butanol), but the selectivity of methacrolein products is low (about 80%), and the byproducts are various and have high content. For the subsequent one-step oxidative esterification of methacrolein to Methyl Methacrylate (MMA), more impurities can affect the conversion rate and selectivity of the reaction, and have a great influence on the reaction stability of the catalyst. The methacrolein product of the isobutylene oxidation needs to be purified and refined more complicated to be further used in the oxidation and esterification process. Therefore, development of a catalyst for preparing methacrolein by oxidizing isobutene with high activity and high selectivity is urgently needed, so that isobutene can be converted into methacrolein with high selectivity, difficulty in a subsequent separation and refining process is reduced, and the reaction performance of an oxidative esterification catalyst is improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a catalyst for preparing methacrolein by selective oxidation of tertiary butanol and isobutene. The catalyst takes gold as a main active component, takes oxides of Mo, bi and Co as main carrier components, and simultaneously adds one or more of oxides of Fe, ce, cu, ni, la, cs, K and the like as auxiliary agents. Gold and oxide support are produced by co-deposition. By introducing a small amount of gold in the preparation process of the catalyst, the reaction temperature of the reaction for preparing the methacrolein by oxidizing the isobutene is greatly reduced, and the selectivity of a reaction product methacrolein is greatly improved.
The catalyst has better conversion rate and extremely high product selectivity in the reaction of preparing the methacrolein by oxidizing the isobutene. The successful development of the catalyst can not only open up the whole flow of the reaction for preparing Methyl Methacrylate (MMA) from isobutene by a two-step method, so that a large amount of isobutene and tertiary butanol which are byproducts in the petroleum refining process are fully utilized, and extremely high economic benefit is created.
One aspect of the invention relates to a catalyst for preparing methacrolein by the selective oxidation of tertiary butanol and isobutene, wherein the supported catalyst comprises an active component and a carrier;
the active component comprises an active element; the active element is Au;
the carrier is a composite metal oxide carrier;
the Au is loaded on the composite metal oxide carrier in the form of nano particles;
the composite metal oxide contains Mo, bi, fe, co, ce, X element;
and X is at least one selected from K, rb, cs, ni, cu.
Optionally, the loading of the active component on the carrier is 0.0001-0.5, wherein the mass of the active component is calculated by the mass of the active metal element;
preferably, the active component is supported on the carrier at a loading of 0.001 to 0.1.
The basic composition of the supported catalyst is as follows:
Au/Mo a Bi b Fe c Co d Ce e X f O m
the a-f represent the atomic ratio of each element; wherein: a=0.1 to 20; b=0.01 to 10; c=0.01 to 5; d=0.1 to 30; e=0.01 to 5; f=0.001 to 5, f varies according to the kind and amount of the auxiliary agent; m=1 to 200.
Preferably, a=0.1 to 2; b=0.01 to 1; c=0.01 to 1; d=0.1 to 3; e=0.01 to 2; f=0.01 to 1; m=1 to 100.
In another aspect, the invention relates to a method for preparing a supported catalyst, the method comprising: and the solution containing the active component, a precursor of molybdenum element, a precursor of bismuth element, a precursor of iron element, a precursor of cobalt element, a precursor of cerium element and a precursor of X element are subjected to coprecipitation to generate the supported catalyst.
Optionally, the method of the supported catalyst comprises the following steps:
(1) Adding a surfactant into a solution containing a gold source, stirring, adding a reducing agent to form a solution I, stirring for 0.2-2 h, and then adding a precursor of molybdenum element to form a solution A;
(2) Mixing raw materials of a bismuth element-containing precursor, an iron element precursor, a cobalt element precursor, a cerium element precursor and an X element precursor with an acidic solution, and stirring at 60 ℃ for half an hour to obtain a solution B;
(3) And mixing the solution B with the solution A, aging, drying and roasting to obtain the supported catalyst.
Optionally, in the step (1),
the gold source is at least one of chloroauric acid, nano gold solution and gold trichloride;
the surfactant is at least one selected from polyvinyl alcohol (PVA), polyethylene glycol and polypropylene glycol;
the reducing agent is at least one selected from sodium borohydride, sodium citrate, tannic acid, ascorbic acid, white phosphorus and sodium borohydride;
the molar ratio of the surfactant to the gold source is 1-1000, and the number of moles of the gold source is calculated by the number of moles of gold elements;
preferably, the molar ratio of the surfactant to the gold source is 1-50;
the mol ratio of the reducing agent to the gold source is 5-50, wherein the mol number of the gold source is calculated by the mol number of gold element;
preferably, the molar ratio of the reducing agent to the gold source is 5-10;
the precursor of the molybdenum element is at least one selected from ammonium molybdate, sodium molybdate or phosphomolybdic acid.
Optionally, in the step (2),
the acid solution is at least one selected from nitric acid solution and tartaric acid solution;
the mass concentration of the nitric acid solution is 5% -15%;
the mass concentration of the tartaric acid solution is 2% -15%;
the precursor of bismuth element is at least one selected from bismuth nitrate, bismuth carbonate, bismuth phosphate and bismuth sulfate;
the precursor of the iron element is at least one selected from ferric nitrate, ferric carbonate, ferric phosphate and ferric sulfate;
the precursor of the cobalt element is at least one selected from cobalt nitrate, cobalt carbonate, cobalt phosphonate and cobalt sulfate;
the precursor of the cerium element is at least one selected from cerium nitrate, cerium carbonate, cerium phosphonate and cerium sulfate;
the precursor of the X element is at least one selected from potassium nitrate, sodium nitrate, potassium carbonate, sodium carbonate, copper nitrate and copper carbonate.
Optionally, in the step (3),
the aging temperature is 60-100 ℃, and the aging time is 3-6 hours; the drying temperature is 100-150 ℃;
the roasting conditions are as follows: roasting in air atmosphere at 500-600 deg.c for 3-5 hr.
In another aspect, the invention relates to a method for preparing methacrolein, which comprises the steps of introducing raw materials and water into a fixed bed reactor filled with a catalyst, and carrying out oxidation reaction in an atmosphere containing oxygen, wherein the catalyst is at least one selected from the supported catalyst and the supported catalyst prepared by the method;
the raw material comprises one of tertiary butanol and isobutene.
Alternatively, the conditions of the reaction are: the reaction temperature is 150-500 ℃, the reaction pressure is 0.05-1 MPa, and the airspeed is 500-20000 h -1 The volume mole ratio of the raw materials, water and oxygen is 1:1-4:7-12.
Preferably, the reaction temperature is 200-360 ℃; the reaction pressure is 0.1-0.3 MPa; the airspeed is 2000-10000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume mole ratio of the raw materials, water and oxygen is 1: 2-3: 8 to 11.
The beneficial effects that this application can produce include:
the catalyst provided by the invention takes gold as a main active component, takes oxides of Mo, bi and Co as main carrier components, reduces the reaction temperature of the reaction for preparing the methacrolein by oxidizing tertiary butanol, and saves energy. In the prior art of the reaction for preparing the methacrolein by oxidizing the tertiary butanol (isobutene), the conversion rate and the selectivity of the catalyst are respectively 85% -92% and 80% -87% at 360-400 ℃, and the catalyst provided by the invention has better conversion rate and extremely high product selectivity in the reaction for preparing the methacrolein by oxidizing the tertiary butanol, and the highest conversion rate and selectivity can respectively reach 93% and 95% at 300-360 ℃, so that the generation of byproducts is reduced, and the purification process of the subsequent reaction is simplified.
Detailed Description
The technical scheme of the present invention is further described below with reference to examples, but the present invention is not limited to these examples.
Unless otherwise specified, the polyvinyl alcohol (PVA) in the examples of the present invention was purchased from Shanghai Ala Biotechnology Co., ltd, had a molecular weight of 44.05, a viscosity of 3.2 to 3.8mPas, and other materials were purchased from China medical group Co., ltd.
In the examples of the present application, the reaction products were analyzed on-line by gas chromatography.
The conversion of isobutene was calculated as follows:
x (isobutylene)% = [1- (amount of unreacted isobutylene substance/amount of supplied isobutylene substance) ]100%
The selectivity calculation method of the methacrolein is as follows:
s (methacrolein)% = [ amount of methacrolein produced/(amount of isobutylene supplied-amount of unreacted isobutylene) ]×100%.
Example 1
And (3) preparing a catalyst: 0.2ml of a 10wt% chloroauric acid solution was added to 30ml of water, followed by adding 30 times by mole of polyvinyl alcohol (PVA) as gold, and stirring for 10 minutes. Sodium borohydride with 20 times of the mole number of gold is quickly added and stirred for 30min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, and the pH of the solution A was measured to be 2. 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of ferric nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate were dissolved in 30ml of a 15% nitric acid solution at 60℃to prepare a solution B. The solution B was slowly added dropwise to the solution A with stirring to obtain a mixed solution. After aging the mixed solution at 80℃for 4 hours, it was evaporated to dryness and dried at 120℃for 4 hours. Finally roasting for 4 hours in an air atmosphere at 550 ℃ to obtain a catalyst A, wherein the composition of the catalyst A is Au 0.1 Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
The catalyst A powder is pressed into particles with 20 to 40 meshes, 1.5ml is taken and is filled into a fixed bed reactor, and the particles are prepared by the method that: water: oxygen=1: 2:10 (molar ratio), space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see Table 1).
Example 2
And (3) preparing a catalyst: 0.02ml of a 10wt% chloroauric acid solution was added to 30ml of water, followed by adding 30 times by mole of PVA to the gold, and stirring for 10 minutes. Rapidly adding sodium borohydride with 20 times of mole number of gold, and stirring30min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, and the pH of the solution A was measured to be 2. 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of ferric nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate were dissolved in 30ml of a 15% nitric acid solution at 60℃to prepare a solution B. The solution B was slowly added dropwise to the solution A with stirring to obtain a mixed solution. After aging the mixed solution at 80℃for 4 hours, it was evaporated to dryness and dried at 120℃for 4 hours. Finally roasting for 4 hours in an air atmosphere at 550 ℃ to obtain a catalyst B, wherein the composition of the catalyst B is Au 0.01 Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
The catalyst B powder is pressed into particles with 20 to 40 meshes, 1.5ml is taken and is filled into a fixed bed reactor, and the particles are prepared by the method that: water: oxygen=1: 2:10 (molar ratio), space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see Table 2).
Example 3
And (3) preparing a catalyst: 0.01ml of a 10wt% chloroauric acid solution was added to 30ml of water, followed by adding 30 times by mole of PVA to the gold, and stirring for 10 minutes. Sodium borohydride with 20 times of the mole number of gold is quickly added and stirred for 30min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, and the pH of the solution A was measured to be 2. 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of ferric nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate were dissolved in 30ml of a 15% nitric acid solution at 60℃to prepare a solution B. The solution B was slowly added dropwise to the solution A with stirring to obtain a mixed solution. After aging the mixed solution at 80℃for 4 hours, it was evaporated to dryness and dried at 120℃for 4 hours. Finally roasting for 4 hours in an air atmosphere at 550 ℃ to obtain a catalyst C, wherein the composition of the catalyst C is Au 0.005 Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
The catalyst C powder is pressed into particles with 20 to 40 meshes, 1.5ml is taken and is filled into a fixed bed reactor, and the particles are prepared by the method that: water: oxygen=1: 2:10 (molar ratio), space velocity of 2500h -1 And at normal pressureThe selective oxidation reaction was carried out under the conditions (see table 3).
Example 4
And (3) preparing a catalyst: 0.01ml of 10wt% chloroauric acid solution was added to 30ml of water, followed by adding PVA 30 times the number of moles of gold, and stirring for 10 minutes. Sodium borohydride with 20 times of the mole number of gold is quickly added and stirred for 30min. Subsequently, 5.45g of ammonium molybdate was dissolved in the above solution to prepare a solution A, and the pH of the solution A was measured to be 2. 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of ferric nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate were dissolved in 30ml of a 15% nitric acid solution at 60℃to prepare a solution B. The solution B was slowly added dropwise to the solution A with stirring to obtain a mixed solution. After aging the mixed solution at 80℃for 4 hours, it was evaporated to dryness and dried at 120℃for 4 hours. Finally roasting for 4 hours in an air atmosphere at 550 ℃ to obtain a catalyst D, wherein the composition of the catalyst D is Au 0.005 Mo 0.1 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.012 O 1 。
The catalyst powder is pressed into particles with 20 to 40 meshes, 1.5ml is taken and is filled into a fixed bed reactor, and the catalyst powder is prepared by the steps of: water: oxygen=1: 2:10 (molar ratio), space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see Table 4).
Comparative example 1
And (3) preparing a catalyst: 10.9g of ammonium molybdate was dissolved in 30ml of aqueous solution to prepare solution A having a ph of 2. 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of ferric nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate were dissolved in 30ml of a 15% nitric acid solution at 60℃to prepare a solution B. Slowly dripping the solution B into the solution A under the stirring state to obtain a mixed solution. After aging the mixed solution at 80℃for 4 hours, it was evaporated to dryness and dried at 120℃for 4 hours. Finally roasting for 4 hours in an air atmosphere at 550 ℃ to obtain a catalyst E, wherein the composition of the catalyst E is Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
The catalyst powder is pressed into particles with 20 to 40 meshes, 1.5ml is taken and packedFeeding into a fixed bed reactor, and adding tert-butanol: water: oxygen=1: 2:10 (molar ratio), space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see Table 5).
TABLE 1 catalytic reactivity of catalyst A
Figure BDA0003152552990000081
TABLE 2 catalytic reactivity of catalyst B
Figure BDA0003152552990000082
TABLE 3 catalytic reactivity of catalyst C
Figure BDA0003152552990000083
Figure BDA0003152552990000091
TABLE 4 catalytic reactivity of catalyst D
Figure BDA0003152552990000092
TABLE 5 catalytic reactivity of catalyst E
Figure BDA0003152552990000093
From tables 1 to 4, it can be seen that in the reaction for synthesizing methacrolein by oxidizing t-butanol (isobutylene), the catalyst activity increases with increasing temperature under the same catalyst conditions, the conversion of t-butanol (isobutylene) increases, the selectivity of methacrolein increases first and then decreases, and the maximum value is reached at the intermediate temperature. The performance of the catalyst can be adjusted by changing the loading capacity of the loaded Au, and the more Au is added, the higher the conversion rate of the catalyst at the same temperature is; when the number of Au atoms is 0.01 (catalyst a and catalyst B), the selectivity of the catalyst is higher at the same temperature.
In combination with the comparison of examples 1 to 3 with comparative example 1, it was found that the conversion of t-butanol (isobutylene) and the selectivity for methacrolein can be improved by adding Au, and the temperature required for the oxidation of t-butanol (isobutylene) to methacrolein is lower and the selectivity for methacrolein is higher at the same activity of the catalyst (i.e., at the same conversion of t-butanol (isobutylene)).
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. A supported catalyst is characterized in that,
the supported catalyst comprises an active component and a carrier;
the active component comprises an active element; the active element is Au;
the carrier is composite metal oxide;
the metal element in the composite metal oxide comprises Mo, bi, fe, co, ce, X;
the X is at least one selected from K, rb and Cs;
the preparation method of the supported catalyst comprises the following steps:
(1) Adding a precursor of molybdenum element into a solution containing a gold source, a surfactant and a reducing agent to form a solution A;
(2) Mixing raw materials of a bismuth-containing precursor, an iron-containing precursor, a cobalt-containing precursor, a cerium-containing precursor and an X-containing precursor with an acidic solution to obtain a solution B;
(3) And mixing the solution B with the solution A, aging, drying and roasting to obtain the supported catalyst.
2. The supported catalyst of claim 1, wherein the supported catalyst has a composition of:
Au/Mo a Bi b Fe c Co d Ce e X f O m
wherein: a=0.1 to 20; b=0.01 to 10; c=0.01 to 5; d=0.1 to 30; e=0.01 to 5; f=0.001 to 5, m=1 to 200.
3. A method of preparing the supported catalyst of any one of claims 1-2, comprising: and the solution containing the active component, a precursor of molybdenum element, a precursor of bismuth element, a precursor of iron element, a precursor of cobalt element, a precursor of cerium element and a precursor of X element are subjected to coprecipitation to generate the supported catalyst.
4. A method according to claim 3, characterized in that it comprises in particular the steps of:
(1) Adding a precursor of molybdenum element into a solution containing a gold source, a surfactant and a reducing agent to form a solution A;
(2) Mixing raw materials of a bismuth-containing precursor, an iron-containing precursor, a cobalt-containing precursor, a cerium-containing precursor and an X-containing precursor with an acidic solution to obtain a solution B;
(3) And mixing the solution B with the solution A, aging, drying and roasting to obtain the supported catalyst.
5. The method of claim 4, wherein in step (1),
the gold source is at least one of chloroauric acid and gold trichloride;
the surfactant is at least one selected from polyvinyl alcohol, polyethylene glycol and polypropylene glycol;
the reducing agent is at least one selected from sodium borohydride, sodium citrate, tannic acid, ascorbic acid and white phosphorus;
the molar ratio of the surfactant to the gold source is 1-1000, wherein the number of moles of the gold source is calculated by the number of moles of gold elements;
the molar ratio of the reducing agent to the gold source is 5-50, wherein the molar number of the gold source is calculated by the molar number of gold element;
the precursor of the molybdenum element is at least one selected from ammonium molybdate, sodium molybdate or phosphomolybdic acid.
6. The method of claim 4, wherein in step (2),
the acid solution is at least one selected from nitric acid solution and tartaric acid solution;
the mass concentration of the nitric acid solution is 5% -15%;
the mass concentration of the tartaric acid solution is 2% -15%;
the precursor of bismuth element is at least one selected from bismuth nitrate and bismuth sulfate;
the precursor of the iron element is selected from at least one of ferric nitrate and ferric sulfate;
the precursor of the cobalt element is at least one selected from cobalt nitrate and cobalt sulfate;
the precursor of the cerium element is at least one selected from cerium nitrate and cerium sulfate;
the precursor of the X element is at least one selected from potassium nitrate and potassium carbonate.
7. The method of claim 4, wherein in step (3),
the aging temperature is 60-100 ℃, and the aging time is 3-6 hours; the drying temperature is 100-150 ℃;
the roasting conditions are as follows: roasting in an air atmosphere at a roasting temperature of 500-600 ℃ for 3-5 hours.
8. A method for preparing methacrolein, characterized in that raw materials and water are introduced into a fixed bed reactor filled with a catalyst, and oxidation reaction is carried out under an atmosphere containing oxygen, wherein the catalyst is at least one selected from the group consisting of the supported catalyst according to any one of claims 1 to 2 and the supported catalyst prepared by the method according to any one of claims 3 to 7;
the raw material is selected from tertiary butanol.
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