CN111203229A - Preparation method and application of supported composite oxide catalyst - Google Patents
Preparation method and application of supported composite oxide catalyst Download PDFInfo
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- CN111203229A CN111203229A CN202010101391.1A CN202010101391A CN111203229A CN 111203229 A CN111203229 A CN 111203229A CN 202010101391 A CN202010101391 A CN 202010101391A CN 111203229 A CN111203229 A CN 111203229A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/8876—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a supported composite metal oxide catalyst for producing methacrolein by isobutene/tertiary butanol. Fully and uniformly mixing a certain amount of metal salt aqueous solution, then carrying out mixed reaction on a coprecipitator under a certain condition, aging and pulping, adding a carrier into the slurry, impregnating under a strengthening condition, separating after impregnation, drying and roasting the impregnated particles under a certain condition to obtain the supported composite metal oxide catalyst. The catalyst provided by the invention has the advantages of simple preparation process and low cost, has excellent catalytic performance in the reaction of producing methacrolein from isobutene/tertiary butanol, and is suitable for industrial application.
Description
Technical Field
The invention relates to a preparation method of a supported composite oxide catalyst, which is applicable to the reaction of producing methacrolein from isobutene/tertiary butanol and belongs to the field of preparation and application of catalysts for producing acrylate chemicals.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material and an industrial intermediate, and is mainly used for producing organic glass, a light guide plate, light guide fibers and the like.
At present, the development of new processes meeting green chemistry requirements is mainly focused on the clean production process of C4, wherein the key step is the synthesis of methacrolein by the oxidation of isobutylene/tert-butanol. The catalyst used in the reaction mainly comprises composite oxides such as Mo-Bi-Fe-Co-O and the like. At present, the activity of the industrial catalyst is lower and the cost is higher, and a plurality of companies and scientific research institutions mainly aim at optimizing components to improve the activity of the catalyst so as to reduce the cost, such as patents sho 55-113730, US5728894, US7012039 and the like.
Disclosure of Invention
The invention provides a preparation method of a metal oxide catalyst with excellent catalytic performance and low cost. In the invention, the utilization rate of the catalyst is improved by loading the macroporous carrier, thereby reducing the cost of the catalyst. The preparation method comprises the steps of adding a macroporous spherical, cylindrical, annular or special-shaped carrier in the preparation process of the catalyst, adsorbing and impregnating metal salts on the inner surface and the outer surface of the carrier under the conditions of vibration, ultrasound and microwave reinforcement, and then roasting, activating and molding to obtain the high-activity supported composite oxide catalyst. The catalyst is used for the reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation, and shows excellent catalytic activity.
The chemical expression of the supported metal oxide catalyst is as follows: mo12BiaFebCocXdYeOmThe carrier is selected from volcanic rock, porous silica gel, α -Al2O3、β-Al2O3、γ-Al2O3One of MCM-41 molecular sieve, KIT-6 molecular sieve, MCM-48, FUD-5, ZSM-5, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve and SBA-15 macroporous carrier.
The preparation process of the catalyst comprises the following steps: fully and uniformly mixing a certain amount of water-soluble metal salt aqueous solution selected from Mo, then mixing a coprecipitator selected from one or more than two of Co, Bi, Fe, Cu, Mg, Ni, V, Ti, Zn, K, Na, Cs, La, Ce, Nd, Zr, Nb, Yb, Er, Sb, Sr and Ag-containing metal salts and a binder selected from one of polyethylene glycol, polyvinyl alcohol, polypropylene glycol and silica sol under a certain condition, ageing and pulping, adding a carrier into the slurry, impregnating under an enhanced condition, separating after impregnation, drying and roasting the impregnated particles under a certain condition to obtain the supported composite oxide catalyst.
The mass ratio of the binder to the precipitant in the step is 1: 100-1: 5, preferably 1: 80-1: 20; the dissolving temperature is 20-100 ℃.
The spherical carrier in the process is selected from volcanic rock, porous silica gel, α -Al2O3、β-Al2O3、γ-Al2O3One of MCM-41 molecular sieve, KIT-6 molecular sieve, MCM-48, FUD-5, ZSM-5, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve and SBA-15 macroporous carrier is preferred, and gamma-Al is preferred2O3MCM-41 molecular sieve and SBA-15 molecular sieve; the shape of the carrier is selected from spherical, cylindrical, annular column and special shape; the mass ratio of the carrier to the metal salt is 3: 1-100: 1; the reaction temperature is 60-100 ℃, the aging temperature is 50-120 ℃, and the time is 1-24 h.
The drying mode in the working procedure can be one of evaporation drying, vacuum drying, microwave drying, suction filtration drying or reduced pressure rotary evaporation drying; the roasting temperature is 350-650 ℃, the heating rate is 1-10 ℃/min, preferably 3-6 ℃/min, and the roasting time is 2-24 h, preferably 4-10 h.
The supported composite metal oxide catalyst prepared by the invention is used for catalyzing isobutene gas phase oxidation in a gas phase to synthesize methacrolein through molecular oxygen in air in a fixed bed.
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 formed methacrolein/(amount of substance of supplied isobutylene-amount of unreacted isobutylene) ] × 100%
In the preparation process of the catalyst, the catalyst can be loaded on the catalyst under the action of materials on the inner surface and the outer surface of the carrier and weak chemical bonds, and the loaded high-efficiency catalyst is obtained through the subsequent drying and roasting process, so that the performance of the catalyst is exerted to the maximum extent. The catalyst is used for synthesizing methacrolein by isobutene gas phase oxidation, and has good catalytic performance. The supported catalyst has the advantages of simple forming mode and low cost, and is suitable for industrial application.
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.
Example 1
Weighing 300ml of deionized water, adding 20g of polyethylene glycol and 330g of ammonium molybdate, and mixing and dissolving to obtain a material A; taking 55g of bismuth nitrate, 45g of ferric nitrate, 172g of cobalt nitrate, 11g of cesium nitrate and 6g of zirconium nitrate, stirring and dissolving in 200ml of deionized water at 40 ℃ to obtain a material B; and slowly adding the material B into the material A placed in a water bath at 45 ℃ under the condition of rapid stirring, immediately adding 800g of spherical alumina after slurry is formed, and refluxing for 8 hours under the ultrasonic action at 60 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 80 ℃, and then placing the catalyst slurry in an air atmosphere at 460 ℃ for 6 hours to roast to obtain the supported composite metal oxide catalyst.
Catalyzing the obtained supported composite metal oxideThe agent is filled in a fixed bed reactor with the inner diameter of 20mm, quartz sand with equal grain diameter is filled above and below the catalyst, and the catalyst is prepared by mixing isobutene: oxygen: the mixed gas of nitrogen gas 1:1.7:12 (molar ratio) is used as raw material, and the space velocity is 2000h-1Reacting at 360 ℃ under normal pressure, continuously reacting for 20 hours, and then carrying out gas chromatography on-line analysis.
It was found that the conversion of isobutylene was 95.3% and the selectivity of MAL was 80.7%.
Example 2
Measuring 300ml of deionized water, adding 9g of polyvinyl alcohol and 220g of ammonium molybdate to obtain a material A, and simultaneously adding 550g of columnar silicon oxide; taking 60g of bismuth nitrate, 16g of copper nitrate, 92g of ferric nitrate, 124g of cobalt nitrate and 12g of cerium nitrate, stirring at 30 ℃ and dissolving in 260ml of deionized water to obtain a material B; and slowly adding the material B into the material A placed in a water bath at 30 ℃ under the condition of rapid stirring to form slurry, and aging for 12 hours under the action of microwaves to obtain the required catalyst slurry.
And (3) carrying out rotary evaporation and evaporation on the obtained catalyst slurry at the temperature of 90 ℃, and then placing the catalyst slurry in an air atmosphere at the temperature of 450 ℃ for 10 hours to carry out roasting to obtain the supported composite metal oxide catalyst.
The catalyst evaluation method was as in example 1.
It was found that the conversion of isobutylene was 95.1% and the selectivity of MAL was 84.1%.
Example 3
Measuring 200ml of deionized water, and adding 40g of polypropylene glycol and 200g of ammonium molybdate to obtain a material A; taking 34g of bismuth nitrate, 172g of cobalt nitrate, 9g of potassium nitrate, 64g of ferric nitrate, 2g of cesium nitrate and 4g of lanthanum nitrate, stirring and dissolving in 200ml of deionized water at 50 ℃ to obtain a material B; weighing 200ml of deionized water, and adding 350g of MCM-41 molecular sieve to obtain a material C; slowly adding the materials A and B into the material C placed in a water bath at 50 ℃ under the supergravity to form slurry, and stirring, aging and refluxing for 10 hours at 100 ℃ to obtain the required catalyst slurry.
And (3) drying the obtained catalyst slurry at 120 ℃ in vacuum, and then placing the catalyst slurry in an air atmosphere at 400 ℃ for 12 hours to carry out roasting to obtain the supported composite metal oxide catalyst.
The catalyst evaluation method was as in example 1.
It was found that the conversion of isobutylene was 97.7% and the selectivity of MAL was 82.3%.
Example 4
200ml of deionized water is measured, 100g of silica sol and 240g of ammonium molybdate are added to obtain a material A, 48g of bismuth nitrate, 112g of cobalt nitrate, 55g of ferric nitrate, 8g of cesium nitrate and 8g of copper nitrate are taken and stirred at 25 ℃ to be dissolved in 200ml of deionized water to obtain a material B, the material B is slowly added into the material A which is placed in a water bath at 50 ℃ under rapid stirring to form slurry, 650g of microspheres β -alumina are added, and the mixture is stirred, aged and refluxed at 100 ℃ for 12 hours to obtain the required catalyst slurry.
And filtering and drying the obtained catalyst slurry, and then placing the catalyst slurry in an air atmosphere at 500 ℃ for 6 hours to carry out roasting to obtain the supported composite metal oxide catalyst.
The catalyst evaluation method was as in example 1.
It was found that the conversion of isobutylene was 94.8% and the selectivity of MAL was 86.5%.
Claims (8)
1. A preparation method of a supported composite oxide catalyst is characterized in that a carrier is added into a metal salt solution in the preparation process of the catalyst, a precipitator and a binder are added for co-impregnation, the uniform impregnation of an active component compound on the surface of the carrier is realized through process reinforcement, and the supported composite oxide catalyst is obtained through drying and roasting under certain conditions.
2. The method according to claim 1, wherein the metal salt is selected from water-soluble compounds of Mo, and the precipitant is selected from one or a combination of two or more of metal salts containing Co, Bi, Fe, Cu, Mg, Ni, V, Ti, Zn, K, Na, Cs, La, Ce, Nd, Zr, Nb, Yb, Er, Sb, Sr, and Ag.
3. The method according to claim 1, wherein the carrier is selected from the group consisting of vesuvianite, porous silica gel, α -Al2O3、β-Al2O3、γ-Al2O3One of MCM-41 molecular sieve, KIT-6 molecular sieve and SBA-15 macroporous carrier.
4. The method according to claim 1, wherein the shape of the carrier is selected from the group consisting of a sphere, a cylinder, and a shape.
5. The method according to claim 1, wherein the impregnation process is one or more process-intensive methods selected from the group consisting of a shaking method, an ultrasonic method, a super-gravity method, and a microwave method.
6. The preparation method according to claim 1, wherein the mass ratio of the binder to the precipitant is 1:100 to 1: 5; the dissolving temperature of the precipitant is 20-100 ℃.
7. The method according to claim 1, wherein the drying step is carried out by a drying method selected from the group consisting of evaporation drying, vacuum drying, microwave drying, suction filtration drying and reduced pressure rotary evaporation drying; the roasting temperature is 350-650 ℃, the heating rate is 1-10 ℃/min, and the roasting time is 2-24 h.
8. A method for synthesizing methacrolein by gas phase oxidation of isobutylene/tert-butanol, characterized by using the supported composite oxide catalyst prepared by the preparation method according to any one of claims 1 to 7.
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Cited By (5)
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| CN113828346A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein and 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 |
| CN114471596A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
| CN114591156A (en) * | 2020-12-07 | 2022-06-07 | 北京水木滨华科技有限公司 | Method for preparing methacrolein and co-producing methacrylonitrile by oxidizing isobutene |
| 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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Cited By (9)
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| CN113828346A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein and preparation method and application thereof |
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| CN114471596A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for preparing catalyst |
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| CN114591156B (en) * | 2020-12-07 | 2024-01-05 | 北京水木滨华科技有限公司 | Method for preparing methacrolein by oxidizing isobutene and co-producing methacrylonitrile |
| 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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