CN114917924A - Catalyst for preparing methylacrolein by selectively oxidizing tert-butyl alcohol and isobutene as well as preparation method and application of catalyst - Google Patents
Catalyst for preparing methylacrolein by selectively oxidizing tert-butyl alcohol and isobutene as well as preparation method and application of catalyst Download PDFInfo
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Abstract
The invention provides a preparation method and application of a catalyst for preparing methacrolein by selectively oxidizing tert-butyl alcohol 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 elements in the composite metal oxide comprise Mo, Bi, Fe, Co, Ce and X elements; and X is selected from at least one of K, Rb, Cs, Ni and Cu. The gold and oxide support are grown by co-deposition. The catalyst is applied to the reaction of preparing methacrolein by selectively oxidizing tert-butyl alcohol (isobutene), can realize the high-efficiency conversion of tert-butyl alcohol (isobutene) to methacrolein at 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
Technical Field
The invention relates to a catalyst for preparing methylacrolein by selectively oxidizing tert-butyl alcohol and isobutene as well as a preparation method and application thereof, belonging to the field of preparation and application of catalysts.
Background
Because of its good physical and chemical properties, Methyl Methacrylate (MMA) is not only an important organic chemical raw material, but also can be directly applied as an organic chemical product, and is widely applied in various industries such as organic glass (PMMA), coatings, leather, and methacrylic acid high-grade esters, and has a very wide market prospect. The traditional process for industrially producing MMA is mainly an acetone cyanohydrin process (ACH process), which uses acetone and virulent hydrocyanic acid as raw materials, and uses highly corrosive sulfuric acid in the reaction process, so that the process has serious environmental pollution and low atom utilization rate.
In recent years, the preparation of MMA by using isobutene (tertiary butanol) as a raw material is widely concerned, and good industrial application prospects are shown due to high atom utilization rate, simple and green process.
The conversion of isobutene into MMA by adopting an isobutene oxidation method is a comprehensive utilization process route of C4 hydrocarbon with low cost, small pollution and good economic benefit. At present, the process routes for preparing MMA by oxidizing isobutene mainly comprise three processes: 1) isobutene is first oxidized to Methacrolein (MAL), then further oxidized to methacrylic acid (MAA), and finally MMA is produced by the esterification process. The route has been industrialized and matured gradually. The catalyst and the process are deeply researched by the China academy of sciences process engineering research institute, Shanghai Huayi (group) company and China petrochemical Shanghai chemical research institute. However, the MMA product can be obtained only through three steps of reaction in the process route, the process flow is long, and the product yield is low. 2) Isobutene is directly oxidized to acrylic acid and then esterified to MMA. The process is simplified and the cost is reduced compared with the first method. But an industrial process has not been achieved. 3) Isobutene is firstly oxidized into methacrolein, and then is subjected to oxidative esterification with methanol to generate MMA. The process also has the advantages of short synthetic route, high atom utilization rate and the like, and has a relatively high industrial application prospect. However, the method is only industrially applied by Asahi Kasei corporation, and no precedent for industrial application exists in China. Therefore, the development of the technology for preparing methyl methacrylate from isobutene, which has independent intellectual property rights at home, has important significance for breaking through the monopoly of foreign technologies and improving the technical level of related fields at home. Meanwhile, the process is simple and green, has little pollution, and has good environmental benefit and richer economic benefit.
The key of the process of preparing methyl methacrylate by isobutene through methacrolein is the research and development of catalysts related to the preparation of methacrolein by selective oxidation of isobutene and the preparation of methyl methacrylate by oxidative esterification of methacrolein. At present, the research group has made a breakthrough progress on the research of the methyl methacrylate catalyst prepared by the oxidation esterification of methacrolein, the catalyst shows excellent catalyst stability and good catalytic performance in the oxidation esterification reaction process of methacrolein, and a series of indexes such as the conversion rate of reactants and the selectivity of products reach or even exceed the level of foreign catalysts.
The catalyst for preparing methacrolein by selective oxidation of isobutene is the Mo-Bi series composite oxide catalyst which is most widely applied at present. Although the catalyst has very good catalytic activity (98%) in the oxidation of isobutene (tertiary butanol), the selectivity of a methacrolein product is low (80%), and the by-products are various and high in content. For the subsequent one-step oxidative esterification of methacrolein to Methyl Methacrylate (MMA), more impurities not only affect the conversion and selectivity of the reaction, but also have a great influence on the reaction stability of the catalyst. The methacrolein product of isobutylene oxidation needs to be purified and refined more complicated for further use in the oxidative esterification process. Therefore, there is a need to develop a catalyst for preparing methacrolein by oxidizing isobutene, which has high activity and high selectivity, so that isobutene can be converted into methacrolein with high selectivity to reduce the difficulty of the subsequent separation and refining process and improve the reaction performance of the oxidation esterification catalyst.
Disclosure of Invention
The invention aims to provide a preparation method and application of a catalyst for selectively oxidizing tertiary butanol and isobutene to prepare methacrolein. The catalyst takes gold as a main active component, takes oxides of Mo, Bi and Co as a main carrier component, and simultaneously adds one or more of oxides of Fe, Ce, Cu, Ni, La, Cs, K and the like as an auxiliary agent. The gold and oxide support are generated in a co-deposition manner. 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 the reaction product methacrolein is greatly improved.
The catalyst has better conversion rate and extremely high product selectivity in the reaction of preparing methacrolein by oxidizing isobutene. The successful development of the catalyst can not only get through the whole process of the reaction for preparing Methyl Methacrylate (MMA) from isobutene in a two-step method, but also make full use of a large amount of isobutene and tertiary butanol which are byproducts in the petroleum refining process, thereby creating extremely high economic benefit.
One aspect of the invention relates to a catalyst for preparing methacrolein by selectively oxidizing 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 a nano-particle form;
the composite metal oxide contains Mo, Bi, Fe, Co, Ce and X;
and X is selected from at least one of K, Rb, Cs, Ni and Cu.
Optionally, the loading amount 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 loading amount of the active component on the carrier is 0.001-0.1.
The supported catalyst basically comprises the following components:
Au/Mo a Bi b Fe c Co d Ce e X f O m
a to f represent the atomic ratio of each element; wherein: a is 0.1-20; b is 0.01 to 10; c is 0.01-5; d is 0.1-30; e is 0.01 to 5; f is 0.001-5, and varies according to the type and quantity of the auxiliary agent; m is 1 to 200.
Preferably, a is 0.1-2; b is 0.01-1; c is 0.01 to 1; d is 0.1 to 3; e is 0.01 to 2; f is 0.01 to 1; m is 1 to 100.
In another aspect, the invention relates to a method of preparing a supported catalyst, the method comprising: and (2) carrying out coprecipitation on a solution containing active components, 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 to generate the supported catalyst.
Optionally, the method of supported catalyst comprises the steps of:
(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 adding a precursor of a molybdenum element to form a solution A;
(2) mixing the raw materials of a precursor containing bismuth, a precursor containing iron, a precursor containing cobalt, a precursor containing cerium and a precursor containing X with an acidic solution, and stirring for half an hour at 60 ℃ 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 selected from chloroauric acid, nano gold solution and gold trichloride;
the surfactant is selected from at least one of polyvinyl alcohol (PVA), polyethylene glycol and polypropylene glycol;
the reducing agent is selected from at least one of 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 molar number of the gold source is calculated by the molar number of the gold element;
preferably, the molar ratio of the surfactant to the gold source is 1-50;
the molar ratio of the reducing agent to the gold source is 5-50, wherein the mole number of the gold source is calculated by the mole number of the gold element;
preferably, the molar ratio of the reducing agent to the gold source is 5-10;
the precursor of the molybdenum element is selected from at least one of ammonium molybdate, sodium molybdate or phosphomolybdic acid.
Optionally, in the step (2),
the acid solution is at least one of 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 the bismuth element is selected from at least one of bismuth nitrate, bismuth carbonate, bismuth phosphate and bismuth sulfate;
the precursor of the iron element is selected from at least one of ferric nitrate, ferric carbonate, ferric phosphate and ferric sulfate;
the precursor of the cobalt element is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt phosphonate and cobalt sulfate;
the precursor of the cerium element is selected from at least one of 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: and roasting in an air atmosphere at the roasting temperature of 500-600 ℃ for 3-5 hours.
In another aspect of the invention, 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 an oxidation reaction under an oxygen-containing atmosphere, wherein the catalyst is selected from at least one of the supported catalyst and the supported catalyst prepared by the method;
the raw material comprises one of tert-butyl alcohol and isobutene.
Optionally, the reaction conditions are: the reaction temperature is 150-500 ℃, the reaction pressure is 0.05-1 MPa, and the space velocity is 500-20000 h -1 The volume molar 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 (ii) a The volume mol ratio of the raw material, water and oxygen is 1: 2-3: 8 to 11.
The beneficial effect that this application can produce includes:
the catalyst provided by the invention takes gold as a main active component and oxides of Mo, Bi and Co as main carrier components, reduces the reaction temperature of the reaction for preparing methacrolein by oxidizing tert-butyl alcohol and saves energy. In the prior art for preparing methylacrolein by oxidizing tertiary butyl alcohol (isobutene), the conversion rate and the selectivity of the catalyst are 85% -92% and 80% -87% respectively at 360-400 ℃, the catalyst of the invention shows better conversion rate and extremely high product selectivity in the reaction for preparing methylacrolein by tertiary butyl alcohol (isobutene), the conversion rate and the selectivity can respectively reach 93% and 95% at the highest temperature of 300-360 ℃, the generation of byproducts is reduced, and the purification process of the subsequent reaction is simplified.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, 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 alading biochemical technology, ltd, molecular weight 44.05, viscosity 3.2-3.8 mPas, and other raw materials were purchased from china pharmaceutical products, ltd, commercially.
In the examples of the present application, the reaction products were analyzed on-line by gas chromatography.
The isobutene conversion was calculated as follows:
x (isobutylene)%, [1- (amount of unreacted isobutylene substance/amount of supplied isobutylene substance) ] × 100%
The selectivity of methacrolein is calculated as follows:
s (methacrolein)% ([ amount of substance of methacrolein produced/(amount of substance of isobutylene supplied — amount of substance of unreacted isobutylene) ] × 100%.
Example 1
Preparing a catalyst: 0.2ml of a 10 wt% chloroauric acid solution was added to 30ml of water, followed by addition of polyvinyl alcohol (PVA) 30 times the mole of gold and stirring for 10 min. Sodium borohydride with the mole number 20 times that of gold is quickly added and stirred for 30 min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, which was measured to have a pH of 2. Taking 2g of bismuth nitrate and 1.9g of nitric acidCerium, 2.0g of iron 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. And slowly dropwise adding the solution B into the solution A under the stirring state to obtain a mixed solution. The mixed solution was aged at 80 ℃ for 4 hours, then evaporated to dryness and dried at 120 ℃ for 4 hours. Finally roasting for 4 hours at 550 ℃ in the air atmosphere to obtain a catalyst A, wherein 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 。
Pressing the catalyst A powder into particles of 20-40 meshes, taking 1.5ml of the particles, filling the particles into a fixed bed reactor, and adding the catalyst A powder into the fixed bed reactor in the proportion of tert-butyl alcohol: water: oxygen 1: 2: 10 (molar ratio) and the space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see table 1).
Example 2
Preparing a catalyst: 0.02ml of 10 wt% chloroauric acid solution was added to 30ml of water, followed by addition of 30 times the molar amount of PVA to gold, and stirring was carried out for 10 min. Sodium borohydride with the mole number 20 times that of gold is quickly added and stirred for 30 min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, which was measured to have a pH of 2. A solution B was prepared by dissolving 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of iron nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate in 30ml of a 15% nitric acid solution at 60 ℃. And slowly dropwise adding the solution B into the solution A under the stirring state to obtain a mixed solution. The mixed solution was aged at 80 ℃ for 4 hours, then evaporated to dryness and dried at 120 ℃ for 4 hours. Finally roasting for 4 hours at 550 ℃ in the air atmosphere to obtain a catalyst B, wherein 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 。
Pressing the catalyst B powder into 20-40 mesh particles, loading 1.5ml of the particles into a fixed bed reactor, and adding the catalyst B powder into a reactor containing tert-butyl alcohol: water: oxygen 1: 2: 10 (molar ratio) and the space velocity of 2500h -1 And the selective oxidation reaction was carried out under the condition of normal pressure (see table 2).
Example 3
Preparing a catalyst: 0.01ml of a 10 wt% chloroauric acid solution was added to 30ml of water, followed by addition of PVA in a 30-fold molar amount to gold, and stirring was carried out for 10 min. And (3) rapidly adding sodium borohydride with the mole number 20 times that of gold, and stirring for 30 min. Subsequently, 10.9g of ammonium molybdate was dissolved in the above solution to prepare a solution A, which was measured to have a pH of 2. A solution B was prepared by dissolving 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of iron nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate in 30ml of a 15% nitric acid solution at 60 ℃. And slowly dropwise adding the solution B into the solution A under the stirring state to obtain a mixed solution. The mixed solution was aged at 80 ℃ for 4 hours, evaporated to dryness and dried at 120 ℃ for 4 hours. Finally roasting for 4 hours at 550 ℃ in the air atmosphere to obtain a catalyst C, wherein the catalyst C comprises Au 0.005 Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
Pressing catalyst C powder into 20-40 mesh particles, loading 1.5ml of the particles into a fixed bed reactor, and adding the catalyst C powder into a reactor with the mass ratio of tert-butyl alcohol: water: oxygen 1: 2: 10 (molar ratio) and the space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see table 3).
Example 4
Preparing a catalyst: 0.01ml of a 10 wt% chloroauric acid solution was added to 30ml of water, followed by addition of PVA in a molar amount 30 times that of gold and stirring for 10 min. And (3) rapidly adding sodium borohydride with the mole number 20 times that of gold, and stirring for 30 min. Subsequently, 5.45g of ammonium molybdate was dissolved in the above solution to prepare a solution A, which was measured to have a pH of 2. A solution B was prepared by dissolving 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of iron nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate in 30ml of a 15% nitric acid solution at 60 ℃. And slowly dropwise adding the solution B into the solution A under the stirring state to obtain a mixed solution. The mixed solution was aged at 80 ℃ for 4 hours, then evaporated to dryness and dried at 120 ℃ for 4 hours. Finally roasting for 4 hours at 550 ℃ in the air atmosphere to obtain a catalyst D, wherein the catalyst D consists of Au 0.005 Mo 0.1 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.012 O 1 。
Pressing the catalyst powder into particles of 20-40 meshes, taking 1.5ml of the particles, filling the particles into a fixed bed reactor, and adding the catalyst powder into the fixed bed reactor in the proportion of tert-butyl alcohol: water: oxygen gas 1: 2: 10 (molar ratio) and the space velocity of 2500h -1 And the selective oxidation reaction was carried out under normal pressure (see table 4).
Comparative example 1
Preparing a catalyst: a solution A having a ph of 2 was prepared by dissolving 10.9g of ammonium molybdate in 30ml of an aqueous solution. A solution B was prepared by dissolving 2g of bismuth nitrate, 1.9g of cerium nitrate, 2.0g of iron nitrate, 8.0g of cobalt nitrate, 0.4g of cesium nitrate and 0.1g of potassium nitrate in 30ml of a 15% nitric acid solution at 60 ℃. The solution B was slowly added dropwise to the solution A while stirring to obtain a mixed solution. The mixed solution was aged at 80 ℃ for 4 hours, evaporated to dryness and dried at 120 ℃ for 4 hours. Finally roasting for 4 hours at 550 ℃ in the air atmosphere to obtain a catalyst E, wherein the catalyst E consists of Mo 0.2 Bi 0.01 Fe 0.04 Co 0.18 Ce 0.04 K 0.01 O 1 。
Pressing the catalyst powder into 20-40 mesh particles, taking 1.5ml of the particles, filling the particles into a fixed bed reactor, and adding the catalyst powder into tert-butyl alcohol: water: oxygen 1: 2: 10 (molar ratio) and the 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
TABLE 2 catalytic reactivity of catalyst B
TABLE 3 catalytic reactivity of catalyst C
TABLE 4 catalytic reactivity of catalyst D
TABLE 5 catalytic reactivity of catalyst E
From tables 1 to 4, it can be seen that in the reaction for synthesizing methacrolein by oxidizing tert-butyl alcohol (isobutylene), under the same catalyst conditions, the catalyst activity increases with the increase of temperature, the conversion rate of tert-butyl alcohol (isobutylene) increases, the selectivity of methacrolein increases and then decreases, and reaches a maximum value at an intermediate temperature. The performance of the catalyst can be adjusted by changing the loading amount 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 catalyst selectivity is higher at the same temperature.
By comparing examples 1 to 3 with comparative example 1, it can be found that the conversion rate of tert-butyl alcohol (isobutylene) and the selectivity of methacrolein can be improved by adding Au, and under the same activity of the catalyst (i.e. under the same conversion rate of tert-butyl alcohol (isobutylene)), the temperature required by the reaction of oxidizing tert-butyl alcohol (isobutylene) into methacrolein is lower, and the selectivity of methacrolein is higher.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A supported catalyst 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 a composite metal oxide;
the metal elements in the composite metal oxide comprise Mo, Bi, Fe, Co, Ce and X;
and X is selected from at least one of K, Rb, Cs, Ni and Cu.
2. The supported catalyst according to claim 1, wherein the loading amount of the active component on the carrier is 0.0001 to 0.5, wherein the mass of the active component is based on the mass of the active metal element;
preferably, the loading amount of the active component on the carrier is 0.001-0.1.
3. The supported catalyst of claim 1, consisting essentially of:
Au/Mo a Bi b Fe c Co d Ce e X f O m
wherein: a is 0.1-20; b is 0.01-10; c is 0.01-5; d is 0.1 to 30; e is 0.01 to 5; f is 0.001 to 5, and m is 1 to 200.
4. A method of preparing a supported catalyst according to any one of claims 1 to 3, comprising: and (2) carrying out coprecipitation on a solution containing active components, 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 to generate the supported catalyst.
5. The method according to claim 4, characterized in that it comprises in particular the steps of:
(1) adding a precursor of molybdenum element into a solution I containing a gold source, a surfactant and a reducing agent to form a solution A;
(2) mixing raw materials of a precursor containing bismuth, a precursor containing iron, a precursor containing cobalt, a precursor containing cerium and a precursor containing X 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.
6. The method according to claim 5, wherein, in step (1),
the gold source is at least one selected from chloroauric acid, nano gold solution and gold trichloride;
the surfactant is selected from at least one of polyvinyl alcohol, polyethylene glycol and polypropylene glycol;
the reducing agent is selected from at least one of 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, wherein the molar number of the gold source is calculated by the molar number of the gold element;
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 the gold element;
the precursor of the molybdenum element is selected from at least one of ammonium molybdate, sodium molybdate or phosphomolybdic acid.
7. The method according to claim 5, wherein, in the step (2),
the acid solution is at least one of 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 the bismuth element is selected from at least one of bismuth nitrate, bismuth carbonate, bismuth phosphate and bismuth sulfate;
the precursor of the iron element is selected from at least one of ferric nitrate, ferric carbonate, ferric phosphate and ferric sulfate;
the precursor of the cobalt element is selected from at least one of cobalt nitrate, cobalt carbonate, cobalt phosphonate and cobalt sulfate;
the precursor of the cerium element is selected from at least one of 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.
8. The method according to claim 5, 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 air atmosphere at 500-600 deg.c for 3-5 hr.
9. A method for preparing methacrolein, characterized in that raw material and water are introduced into a fixed bed reactor filled with a catalyst, and an oxidation reaction is carried out in 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 3 and the supported catalyst prepared by the method according to any one of claims 4 to 8;
the raw material is selected from one of tert-butyl alcohol and isobutene.
10. The method of claim 9,
the conditions of the oxidation reaction are as follows: the reaction temperature is 150-500 ℃, the reaction pressure is 0.05-1 MPa, and the space velocity is 500-20000 h -1 The volume molar 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 (ii) a Of raw materials, water, oxygenThe volume mol ratio is 1: 2-3: 8 to 11.
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| CN1087290A (en) * | 1992-06-25 | 1994-06-01 | Basf公司 | Multimetal oxide compositions |
| CN102371157A (en) * | 2010-08-04 | 2012-03-14 | 日本化药株式会社 | Methyl Acraldehyde, Catalyst Used For Preparing Methyl Acraldehyde And Preparation Method Thereof |
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