CN111389410A - Composite metal oxide catalyst and preparation method thereof - Google Patents
Composite metal oxide catalyst and preparation method thereof Download PDFInfo
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- CN111389410A CN111389410A CN202010307354.6A CN202010307354A CN111389410A CN 111389410 A CN111389410 A CN 111389410A CN 202010307354 A CN202010307354 A CN 202010307354A CN 111389410 A CN111389410 A CN 111389410A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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Abstract
The invention relates to a composite metal oxide catalyst for the reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation. The catalyst consists of a main catalyst composite metal oxide and a doped composite metal oxide, and the doped composite metal oxide is added in the preparation or forming process of the main catalyst composite metal oxide, so that the aim of selectively improving the performance of the catalyst is fulfilled. The catalyst provided by the invention has the advantages of simple preparation process and strong pertinence, has excellent catalytic performance in the reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation, and is suitable for industrial production.
Description
Technical Field
The invention relates to a composite metal oxide catalyst and a preparation method thereof, and the catalyst is particularly suitable for the reaction of preparing methacrolein by selective oxidation of isobutene/tertiary butanol. The catalyst is prepared by mixing the main composite metal oxide and the doped composite metal oxide in the preparation or forming process, and has high catalytic activity and stability. The invention belongs to the field of catalyst preparation and application.
Background
Methacrolein (MA L) is an important organic chemical product, the acetone cyanohydrin method (ACH method) which is a traditional high-pollution and high-cost production process is gradually replaced by the C4 method which is an existing green production process, in the C4 method process, isobutene/tert-butyl alcohol is used as a raw material, and partial oxidation is carried out on composite metal oxides containing molybdenum, bismuth, cobalt and the like to generate methacrolein.
At present, the main production process of the catalyst used in the reaction is a coprecipitation process, and the catalyst is formed into particles, solid columns, hollow columns and spheres by different forming processes and then applied to the production process of the methacrolein so as to achieve the aim of improving the selectivity of the methacrolein. For example, the patents US4511671, CN1199729C and CN102371157A utilize the change of the preparation and forming method of the catalyst to improve the reaction performance of the catalyst. At first, researchers have also improved the catalyst performance by adding organic substances, new auxiliary agents or changing the types and the amounts of the auxiliary agents. For example, patent 103157468A, JP 6(1994) -381A, 103157484A, CN102989470A, 01111960.8, etc. obtain higher activity by changing the kind and amount of auxiliary agent, adding proper organic matter, changing calcination temperature, etc., respectively, but inevitably generate phenomena of high conversion rate and low conversion rate or high selectivity and low conversion rate.
Accordingly, there is a need in the art to develop an improved method for preparing an existing catalyst, which has high activity and selectivity.
Disclosure of Invention
The invention aims to provide a composite metal oxide catalyst, which consists of a main catalyst composite metal oxide and a doped composite metal oxide, is suitable for the reaction of preparing methacrolein by selective oxidation of isobutene/tertiary butanol, and has high activity and high selectivity.
Another objective of the present invention is to provide a composite metal oxide catalyst and a preparation method thereof, wherein the preparation method is to selectively increase the activity or selectivity of the catalyst by adding one or more doped composite metal oxides in a targeted manner during the preparation or molding process of a composite metal oxide using Mo, Bi, Fe, and Co as a main catalyst.
Accordingly, one aspect of the present invention relates to a method for preparing a composite metal oxide having a specific general formula:
x(Mo11BiaFebCocXdYeZfOm)/y(MoAgOn)
wherein X is one or more selected from Ru, Sb, Cr, Sr, Ag, As, Pd and Mg;
y is one or more selected from alkaline earth metal or alkali metal;
z is one or more selected from L a, Ce, Pr, Eu, Nd, Zr, Ti, Nb, Yb and Er;
a is selected from one of Bi, Mn, Co, Pb, Fe, Ni, Ca, Zn and Cu;
a. b, c, d, e, m, n represent the atomic ratio of each element, respectively, wherein,
a is selected from 0-6;
b is selected from 0-5;
c is selected from 0-10;
d is selected from 0.2-6;
e is selected from 0.1 to 7;
f is selected from 0.1-6;
g is selected from 0-10;
m and n are oxygen atoms satisfying the oxidation state of the elements;
x and y respectively represent the amount of the composite metal oxide of the main catalyst and the doped composite metal oxide, and the mass ratio of y/x is more than or equal to 0 and less than or equal to 3.0.
The composite metal oxide catalyst is composed of a main catalyst composite metal oxide and a doped composite metal oxide, and the mass ratio of the doped composite metal oxide to the main catalyst composite metal oxide is 0.01-3.0.
The preparation method of the main catalyst composite metal oxide is selected from a coprecipitation method and a step precipitation method, and the preparation method of the doped composite metal oxide is selected from a precipitation method, a hydrothermal method, a solvothermal method, a microwave hydrothermal method, a molten salt method and a spray drying method, preferably the precipitation method and the hydrothermal method.
Another aspect of the invention relates to a method for preparing a composite metal oxide, wherein the mixing mode of the component main catalyst composite metal oxide and the doped composite metal oxide adopts any one or more of the following modes:
(1) preparing mixed metal salt required by the composite metal oxide of the main catalyst into a solution, marking the mixed metal salt as A, preparing metal salt required by the doped composite metal oxide into a solution, marking the solution as B, and adding the A and the B into a precipitator together to obtain coprecipitation;
(2) preparing mixed metal salt required by the composite metal oxide of the main catalyst into a solution, marking the solution as C, preparing metal salt required by the doped composite metal oxide into a solution, marking the solution as D, respectively adding a precipitator into the solution C and the solution D, mixing the two precipitates according to a certain proportion after the precipitates are completely precipitated, and then aging;
(3) preparing a solution of mixed metal salts required by the composite metal oxide of the main catalyst, namely E, preparing a solution of metal salts required by the doped composite metal oxide, namely F, adding a precipitator into the solution of E and the solution of F respectively to obtain precipitates, and mixing the precipitates according to a certain proportion after the precipitates are aged and dried;
(4) preparing mixed metal salt required by the composite metal oxide of the main catalyst into solution G, preparing metal salt required by the doped composite metal oxide into solution H, adding a precipitator into the solution G and the solution H respectively to obtain precipitates, and mixing the precipitates according to a certain proportion after the precipitates are aged, dried and roasted.
Wherein the drying modes of the two materials can be one or more of evaporation drying, rotary evaporation drying, suction filtration drying, blast drying, vacuum drying, microwave drying and spray drying, and the drying temperature is 50-220 ℃. The mixing mode of the main catalyst composite metal oxide and the doped composite metal oxide can be one or more of stirring mixing, shaking mixing, ultrasonic mixing, kneading mixing, pneumatic mixing and impulsive mixing.
The composite metal oxide catalyst is suitable for the reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation in a fixed bed reaction system.
In the present invention, the conversion of isobutylene and the selectivity of methacrolein are defined as follows:
the conversion of isobutene is defined as follows:
x (isobutylene)%, the amount of isobutylene substance participating in the reaction/the amount of isobutylene substance supplied × 100%
The selectivity of methacrolein is defined as follows:
s (methacrolein)% (amount of substance of generated methacrolein/amount of substance of isobutene participating in the reaction) × 100% the composite metal oxide catalyst of the present invention is composed of a main catalyst composite metal oxide and a doped composite metal oxide, wherein the doped composite metal oxide is added in the preparation or forming process of the main catalyst composite metal oxide, so that the catalyst activity or selectivity is selectively improved.
Detailed Description
The present invention is illustrated below by way of examples, but the scope of the present invention is not limited by the examples.
Weighing 26g of bismuth nitrate, 41g of ferric nitrate, 12g of cobalt nitrate, 6g of cesium nitrate and 3g of lanthanum nitrate, and stirring and dissolving the materials in 100ml of dilute nitric acid solution with the concentration of 5% at 35 ℃ to obtain a material A; weighing 52g of cobalt nitrate, stirring at normal temperature and dissolving in 50ml of deionized water to obtain a material B; measuring 150ml of deionized water, adding 280g of ammonium molybdate, and stirring and dissolving at 45 ℃ to obtain a material C; and (3) slowly dripping the materials A and B into the material C placed in a water bath at 45 ℃ under the condition of rapid stirring to form slurry, and stirring, aging and refluxing for 8 hours at 65 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 90 ℃ to dryness, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 420 ℃ for 8 hours to roast to obtain the composite metal oxide catalyst powder.
Tabletting the catalyst powder, and pulverizing to 40-80 mesh.
2.0 ml of the obtained 20-40 mesh composite metal oxide catalyst is mixed with quartz sand with equal particle size according to the volume ratio of 1:1 and is filled in a fixed bed reactor with the inner diameter of 10mm, the upper part and the lower part of the catalyst are filled with the quartz sand with equal particle size, and the mixture is prepared by mixing isobutene: oxygen: the mixed gas of nitrogen gas 1:2.1:12 (molar ratio) is used as raw material, and the space velocity is 2000h-1Reacting at 360 ℃ under normal pressure for 20 hours continuously and then carrying out gas chromatography on-line analysis.
It was found that the conversion of isobutene was 97.3% and the selectivity for MA L was 82.9%.
Example 2
Weighing 6g of bismuth nitrate, 2g of potassium nitrate, 39g of ferric nitrate, 71g of cobalt nitrate, 11g of cesium nitrate and 5g of cerium nitrate, and stirring and dissolving in 100ml of 3% dilute nitric acid solution at 40 ℃ to obtain a material A; measuring 100ml of deionized water, adding 140g of ammonium molybdate, and dissolving at 50 ℃ to obtain a material B; slowly adding the material A into the material B placed in a water bath at 50 ℃ under the condition of rapid stirring to obtain slurry C; weighing 32g of bismuth nitrate, stirring and dissolving in 100ml of 10% dilute nitric acid solution at 25 ℃ to obtain a material D; measuring 50ml of deionized water, adding 25g of ammonium molybdate, dissolving at 40 ℃ to obtain a material E, and slowly adding the material D into the material E placed in a water bath at 40 ℃ under rapid stirring to obtain slurry F; slurry F was added to slurry C over 30 minutes with rapid stirring at 80 ℃ and then aged under stirring at 80 ℃ for 12 hours under reflux to give the desired catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 80 ℃, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 450 ℃ for 9 hours to roast to obtain the composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 98.7% and the selectivity for MA L was 84.4%.
Example 3
Weighing 22g of bismuth nitrate, 9g of copper nitrate, 39g of ferric nitrate, 3g of cesium nitrate, 4g of cerium nitrate and 1g of lithium carbonate, and stirring and dissolving the materials in 150ml of 10% dilute nitric acid solution at the temperature of 40 ℃ to obtain a material A; measuring 200ml of deionized water, adding 150g of ammonium molybdate, and dissolving at 30 ℃ to obtain a material B; slowly adding the material A into the material B placed in a water bath at 60 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 10 hours at 80 ℃ to obtain the required slurry.
Stirring and evaporating the obtained slurry at 100 ℃, crushing the obtained solid, placing the crushed solid in an air atmosphere at 500 ℃ for 5 hours, and roasting to obtain the main catalyst composite metal oxide powder C.
Weighing 114g of cobalt nitrate, stirring at 30 ℃ and dissolving in 100ml of deionized water to obtain a material D; measuring 100ml of deionized water, adding 65g of ammonium molybdate, and dissolving to obtain a material E; and slowly adding the material D into the material E placed in a water bath at 50 ℃ under rapid stirring, adding 80ml of Dimethylformamide (DMF) to form slurry after dropwise addition is completed, and stirring, aging and refluxing for 12 hours at 60 ℃ to obtain the required slurry.
And washing and filtering the obtained slurry, drying the slurry in a vacuum drying oven at 70 ℃ for 12 hours, crushing the obtained solid, standing the crushed solid in an air atmosphere at 400 ℃ for 6 hours, and roasting to obtain the doped composite metal oxide powder F.
And fully oscillating 50g of the main catalyst composite metal oxide powder C and 3g of the doped composite metal oxide powder F for 5 hours under the action of an oscillator to obtain the required composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 98.6% and the selectivity for MA L was 82.1%.
Example 4
Weighing 8g of bismuth nitrate, 136g of cobalt nitrate, 44g of ferric nitrate, 2g of sodium nitrate, 6g of lanthanum nitrate and 3g of cerium nitrate, stirring at normal temperature, and dissolving in 150ml of 5% dilute nitric acid solution to obtain a material A; measuring 150ml of deionized water, adding 150g of ammonium molybdate, and dissolving at 45 ℃ to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 45 ℃ under the condition of rapid stirring, and stirring, aging and refluxing the formed slurry for 10 hours at 85 ℃ to obtain the required slurry.
Stirring and evaporating the obtained slurry at 85 ℃ to dryness, crushing the obtained solid, placing the crushed solid in an air atmosphere at 450 ℃ for 6 hours to roast to obtain the main catalyst composite metal oxide powder C.
Weighing 98g of bismuth nitrate, stirring and dissolving in 150ml of 5% dilute nitric acid solution at 40 ℃ to obtain a material D, weighing 100ml of 0.5 mol/L NaOH solution, adding 38g of ammonium molybdate, dissolving to obtain a material E, slowly adding the material D into the material E placed in a 60 ℃ water bath under rapid stirring, aging and refluxing for 6 hours at 60 ℃, transferring the aged material into a high-pressure lining tetrafluoro reaction kettle, reacting for 12 hours at 160 ℃, and naturally cooling to obtain the required slurry.
And washing and filtering the obtained slurry, placing the slurry in a forced air drying oven at 120 ℃ for drying for 12 hours, crushing the obtained solid, placing the crushed solid in an air atmosphere at 480 ℃ for staying for 8 hours, and roasting to obtain doped composite metal oxide powder F.
And fully mixing 40g of the main catalyst composite metal oxide powder C and 8g of the doped composite metal oxide powder F for 2 hours under the action of pneumatic mixing to obtain the required composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 99.8% and the selectivity for MA L was 85.3%.
Example 5
Weighing 32g of bismuth nitrate, 5g of ferric nitrate, 83g of cobalt nitrate, 4g of cesium nitrate, 6g of lanthanum nitrate and 2g of cerium nitrate, and stirring and dissolving in 100ml of 10% dilute nitric acid solution at the temperature of 30 ℃ to obtain a material A; measuring 100ml of deionized water, adding 140g of ammonium molybdate, and dissolving at 40 ℃ to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 40 ℃ under the condition of rapid stirring, and stirring, aging and refluxing the obtained slurry for 18 hours at 70 ℃ to obtain the required slurry.
Stirring and evaporating the obtained slurry at 80 ℃, and crushing to obtain the main catalyst composite metal oxide precursor powder C.
Weighing 36g of ferric nitrate, stirring at 35 ℃ and dissolving in 100ml of deionized water to obtain a material D; 50ml of deionized water is measured, 22g of ammonium molybdate is added, the mixture is dissolved at 40 ℃ to obtain a material E, the material D is slowly added into the material E placed in a water bath at 40 ℃ under rapid stirring, and the obtained slurry is stirred and refluxed at 80 ℃ for 6 hours to obtain the required slurry.
And washing and filtering the obtained slurry, drying the slurry in an air-blast drying oven at the temperature of 80 ℃, and crushing the dried slurry to obtain the doped metal oxide precursor powder F.
And fully mixing the obtained 60g of main catalyst composite metal oxide precursor powder C and 2g of doped composite metal oxide powder F for 4 hours under the action of mechanical stirring to obtain the required composite metal oxide catalyst precursor powder.
Placing the obtained composite metal oxide catalyst precursor powder in a nitrogen atmosphere at 500 ℃ for 3 hours, and then in an air atmosphere at 450 ℃ for 6 hours for roasting.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 99.1% and the selectivity for MA L was 81.9%.
Comparative example 1
Referring to the composite metal oxide catalyst prepared in example 2, except that bismuth nitrate was not added in the process of preparing the material a, the desired composite metal oxide catalyst powder was obtained.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 96.4% and the selectivity for MA L was 83.9%.
Comparative example 2
Referring to the composite metal oxide catalyst prepared in example 3, 32g of cobalt nitrate was added in the process of preparing the material a to obtain the desired composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 99.0% and the selectivity for MA L was 84.6%.
Comparative example 3
Referring to the composite metal oxide catalyst prepared in example 3, only 3g of the doped composite metal oxide powder F was changed to 5g of the doped composite metal oxide powder F to obtain a desired composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 99.7% and the selectivity for MA L was 82.1%.
Comparative example 4
Referring to the composite metal oxide catalyst prepared in example 4, the material D was slowly added to the material E placed in a 60 ℃ water bath under rapid stirring, after completion of the dropwise addition, the mixture was stirred, aged and refluxed for 6 hours at 60 ℃, the aged material was transferred to a tetrafluoro reaction kettle with a high-pressure liner to react for 12 hours at 160 ℃, and after natural cooling, the required slurry was obtained by instead slowly adding the material D to the material E placed in a 60 ℃ water bath under rapid stirring, after completion of the dropwise addition, the mixture was stirred, aged and refluxed for 6 hours at 60 ℃ to obtain the required slurry, and the required composite metal oxide catalyst powder was obtained through the same procedures of washing, suction filtration, drying and calcination as in example 4.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 97.3% and the selectivity for MA L was 85.9%.
The above examples show that the preparation method of the composite metal oxide catalyst of the present invention is simple, and the performance of the catalyst can be selectively improved by adding the doped composite metal oxide in the preparation or molding process of the main catalyst composite metal oxide, and the flexibility is high. The catalyst prepared by the method has higher activity and selectivity when the isobutene/tertiary butanol is selectively oxidized to prepare the methacrolein, and is suitable for industrial amplification.
Claims (8)
1. A method for preparing a composite metal oxide, characterized in that the specific general formula of the composite metal oxide is:
x(Mo11BiaFebCocXdYeZfOm)/y(MoAgOn)
wherein X is one or more selected from Ru, Sb, Cr, Sr, Ag, As, Pd and Mg;
y is one or more selected from alkaline earth metal or alkali metal;
z is one or more selected from L a, Ce, Pr, Eu, Nd, Zr, Ti, Nb, Yb and Er;
a is selected from one of Bi, Mn, Co, Pb, Fe, Ni, Ca, Zn and Cu;
a. b, c, d, e, m, n represent the atomic ratio of each element, respectively, wherein,
a is selected from 0-6;
b is selected from 0-5;
c is selected from 0-10;
d is selected from 0.2-6;
e is selected from 0.1 to 7;
f is selected from 0.1-6;
g is selected from 0-10;
m and n are oxygen atoms satisfying the oxidation state of the elements;
x and y respectively represent the amount of the composite metal oxide of the main catalyst and the doped composite metal oxide, and the mass ratio of y/x is more than or equal to 0.01 and less than or equal to 3.0.
2. The method for preparing a composite metal oxide catalyst according to claim 1, wherein the composite metal oxide catalyst comprises a main catalyst composite metal oxide and a doped composite metal oxide, and the mass ratio of the doped composite metal oxide to the main catalyst composite metal oxide is 0.01 to 3.0.
3. The method for preparing a composite metal oxide catalyst according to claim 2, wherein the method for preparing the main catalyst composite metal oxide is selected from a coprecipitation method and a fractional precipitation method.
4. The method of preparing the composite metal oxide catalyst according to claim 2, wherein the method of preparing the doped composite metal oxide is selected from the group consisting of precipitation, hydrothermal, solvothermal, microwave hydrothermal, molten salt, and spray-drying methods, preferably precipitation and hydrothermal methods.
5. The method for producing a composite metal oxide catalyst according to any one of claims 2 to 4, characterized in that: the mixing mode of the main catalyst composite metal oxide and the doped composite metal oxide adopts any one or more of the following modes:
(1) preparing mixed metal salt required by the composite metal oxide of the main catalyst into a solution, marking the mixed metal salt as A, preparing metal salt required by the doped composite metal oxide into a solution, marking the solution as B, and adding the A and the B into a precipitator together to obtain coprecipitation;
(2) preparing mixed metal salt required by the composite metal oxide of the main catalyst into a solution, marking the solution as C, preparing metal salt required by the doped composite metal oxide into a solution, marking the solution as D, respectively adding a precipitator into the solution C and the solution D, mixing the two precipitates according to a certain proportion after the precipitates are completely precipitated, and then aging;
(3) preparing a solution of mixed metal salts required by the composite metal oxide of the main catalyst, namely E, preparing a solution of metal salts required by the doped composite metal oxide, namely F, adding a precipitator into the solution of E and the solution of F respectively to obtain precipitates, and mixing the precipitates according to a certain proportion after the precipitates are aged and dried;
(4) preparing mixed metal salt required by the composite metal oxide of the main catalyst into solution G, preparing metal salt required by the doped composite metal oxide into solution H, adding a precipitator into the solution G and the solution H respectively to obtain precipitates, and mixing the precipitates according to a certain proportion after the precipitates are aged, dried and roasted.
6. The method for preparing a composite metal oxide catalyst according to any one of claims 2 to 5, wherein the drying manner of the material is one or more selected from evaporation drying, rotary evaporation drying, suction filtration drying, forced air drying, vacuum drying, microwave drying and spray drying, and the drying temperature is 50-220 ℃.
7. The method for preparing a composite metal oxide catalyst according to any one of claims 2 to 5, wherein the two materials are mixed by one or more selected from the group consisting of stirring, shaking, ultrasonic mixing, kneading, pneumatic mixing and impulse mixing.
8. The method of producing a composite metal oxide catalyst according to any one of claims 2 to 7, wherein the composite metal oxide catalyst is used for producing methacrolein by oxidation of isobutylene or tert-butanol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112675866A (en) * | 2020-12-24 | 2021-04-20 | 烟台大学 | Composite metal oxide catalyst, preparation method and application thereof |
| CN114054100A (en) * | 2020-08-06 | 2022-02-18 | 中国科学院过程工程研究所 | Preparation and application of doped composite oxide catalyst |
| CN114917924A (en) * | 2021-07-07 | 2022-08-19 | 中国科学院大连化学物理研究所 | Catalyst for preparing methylacrolein by selectively oxidizing tert-butyl alcohol and isobutene as well as preparation method and application of catalyst |
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| CN104437533A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst of methacrylaldehyde and methacrylic acid, as well as preparation method of catalyst for synthesizing methacrylaldehyde and methacrylic acid |
| CN103816917A (en) * | 2014-03-14 | 2014-05-28 | 厦门大学 | Propylene selective-oxidation prepared acrolein catalyst and preparation method thereof |
| CN110227482A (en) * | 2018-03-05 | 2019-09-13 | 上海华谊新材料有限公司 | Composite oxide catalysts and preparation method thereof |
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| CN114054100A (en) * | 2020-08-06 | 2022-02-18 | 中国科学院过程工程研究所 | Preparation and application of doped composite oxide catalyst |
| CN114054100B (en) * | 2020-08-06 | 2023-01-10 | 中国科学院过程工程研究所 | Preparation and application of doped composite oxide catalyst |
| CN112675866A (en) * | 2020-12-24 | 2021-04-20 | 烟台大学 | Composite metal oxide catalyst, preparation method and application thereof |
| CN114917924A (en) * | 2021-07-07 | 2022-08-19 | 中国科学院大连化学物理研究所 | Catalyst for preparing methylacrolein by selectively oxidizing tert-butyl alcohol and isobutene as well as preparation method and application of catalyst |
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