CN113387908A - Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene - Google Patents

Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene Download PDF

Info

Publication number
CN113387908A
CN113387908A CN202110600733.9A CN202110600733A CN113387908A CN 113387908 A CN113387908 A CN 113387908A CN 202110600733 A CN202110600733 A CN 202110600733A CN 113387908 A CN113387908 A CN 113387908A
Authority
CN
China
Prior art keywords
styrene
catalyst
reaction
magnesium
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110600733.9A
Other languages
Chinese (zh)
Other versions
CN113387908B (en
Inventor
刘江永
纪兴洋
王理霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou University
Original Assignee
Yangzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou University filed Critical Yangzhou University
Priority to CN202110600733.9A priority Critical patent/CN113387908B/en
Publication of CN113387908A publication Critical patent/CN113387908A/en
Application granted granted Critical
Publication of CN113387908B publication Critical patent/CN113387908B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an application of magnesium cobaltate in styrene selective oxidation reaction. The specific catalytic reaction process is as follows: styrene, tert-butyl hydroperoxide and solvent are mixed evenly, magnesium cobaltate is added, and the product of styrene oxide is obtained after reaction for a period of time at a certain temperature. The magnesium cobaltate catalytic material is cheap and easy to obtain, the catalytic reaction system is mild in condition, simple and easy to control, good in reaction effect and stable in performance, and is beneficial to large-scale popularization.

Description

Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene
Technical Field
The invention relates to an application of a magnesium cobaltate catalyst in selective oxidation reaction of styrene, belonging to the technical field of catalytic oxidation reaction of olefin.
Background
Styrene oxide is an important fine chemical and is widely applied. In recent years, heterogeneous catalytic oxidation processes using styrene as a starting material and a green oxidant have been widely noticed and studied. For example, the literature (ACS Catalysis, 2017, 7, 3483-The styrene conversion was 25.3% and the styrene oxide selectivity was 93.2%. Literature (Journal of Energy Chemistry, 2017, 26, 681-687) Zr-doped CeO2The nano particles are used for styrene oxidation, tert-butyl hydroperoxide is used as an oxidant, and after 12 hours of reaction, the conversion rate of styrene is 78.1%, and the selectivity of styrene oxide is 79.3%. Literature (Nanoscale Advances, 2020, 2, 1437) confines Au to mesoporous SiO2The catalyst is used in the styrene oxidation reaction with tert-butyl hydroperoxide as oxidant, and after the reaction is carried out for 12 hours under the optimal reaction condition, the conversion rate of the styrene reaches 88.0 percent, and the selectivity of the styrene oxide is 74.0 percent. Literature (ACS Sustainable Chemistry)&Engineering, 2019, 7, 17008-2/g-C3N4The composite catalyst is used in the styrene oxidation reaction with tert-butyl hydroperoxide as oxidant and 8MnO is found through screening2The NP/UCN catalyst has the best catalytic performance, the conversion rate of styrene is 78.3%, and the selectivity of epoxyphenylethane is 77.6%. Although numerous catalysts have been reported, the current challenge in this field is to find a catalyst that is simple to prepare, inexpensive, and has excellent reaction properties.
Magnesium cobaltate has the advantages of easy preparation, low price and the like, and has been researched to be used as a catalytic material recently, so that a satisfactory reaction effect is achieved. For example, the literature (Chemical Engineering Journal, 2021, 405, 126907) uses magnesium cobaltate for the reaction of carbon dioxide and epoxy to produce cyclic carbonate; the patent (CN 108906063 a) uses magnesium cobaltate to catalyze peroxymonosulfate for removing organic pollutants; the patent (CN 107335437 a) uses magnesium cobaltate for the decomposition of nitrous oxide off-gas in high concentrations. At present, no report is available on the application of magnesium cobaltate in the selective oxidation reaction of styrene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the application of the magnesium cobaltate catalyst in the selective oxidation reaction of styrene, the catalytic system is easy to control, the reaction effect is good, the performance is stable, and the large-scale popularization is facilitated.
In order to solve the technical problems, the invention provides an application of a magnesium cobaltate catalyst in selective oxidation reaction of styrene.
Further, the reaction process comprises the following steps: styrene, tert-butyl hydroperoxide and solvent are evenly mixed, magnesium cobaltate catalyst is added, and the product of styrene oxide is obtained after reaction.
Further, the solvent is acetonitrile.
Further, the amount of the magnesium cobaltate catalyst is 3.2-12.8 wt.% of styrene.
Further, the mass ratio of the styrene to the tert-butyl hydroperoxide to the solvent is 1:4: 18.8.
Further, the reaction temperature is 70-90 ℃.
Further, the reaction time is 7-10 h.
Further, the preparation method of the magnesium cobaltate catalyst comprises the following steps: weighing magnesium nitrate hexahydrate and cobalt nitrate hexahydrate, dissolving in deionized water, adding urea into the solution, stirring, transferring the solution into a hydrothermal kettle, keeping the temperature at 120 ℃ and 200 ℃ for 6-18 h, cooling to room temperature, filtering, washing with deionized water and ethanol, drying, and calcining to obtain the magnesium cobaltate catalyst.
Further, the mass ratio of the magnesium nitrate hexahydrate to the cobalt nitrate hexahydrate to the urea is 1:2.23: 2.34.
Further, the drying temperature is 50-120 ℃, and the drying time is 6-18 h; the calcination temperature is 400-600 ℃, and the calcination time is 1-4 h.
The invention achieves the following beneficial effects:
(1) the magnesium cobaltate catalyst is easy to prepare, low in price and easy to obtain;
(2) the catalytic system is easy to control, has good reaction effect and stable performance, and is beneficial to large-scale popularization.
Drawings
FIG. 1 shows a magnesium cobaltate catalyst (MgCo) prepared in inventive example 12O4) And MgO in comparative example 1 and Co in comparative example 23O4XRD pattern of (a).
FIG. 2 is MgCo prepared in inventive example 12O4SEM image of catalyst.
Fig. 3 is an SEM image of the MgO catalyst according to inventive comparative example 1.
FIG. 4 shows Co prepared in comparative example 2 of the invention3O4SEM image of catalyst.
FIG. 5 is MgCo prepared in inventive example 12O4TEM images of the catalyst.
FIG. 6 is MgCo prepared in inventive example 12O4HRTEM image of catalyst.
Detailed Description
The invention is further described below with reference to the figures and examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Weighing 2 mmol of magnesium nitrate hexahydrate and 4 mmol of cobalt nitrate hexahydrate, dissolving in 50 mL of deionized water, adding 1.2 g of urea into the solution, stirring for half an hour, transferring the solution into a hydrothermal kettle, keeping the temperature at 180 ℃ for 12 hours, cooling to room temperature, filtering, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours; and (3) calcining the obtained sample at 500 ℃ for 2 h to obtain the magnesium cobaltate catalyst. FIG. 1 contains MgCo prepared in example 12O4XRD pattern of catalyst. FIG. 2 is MgCo prepared in example 12O4SEM image of catalyst. FIG. 5 is MgCo prepared in example 12O4TEM images of the catalyst. FIG. 6 is MgCo prepared in example 12O4HRTEM image of catalyst.
The prepared catalyst is used for the selective oxidation reaction of styrene. First, 15 mmol of styrene, 45 mmol of t-butyl hydroperoxide and 16 mL of acetonitrile were mixed, and then reacted at 80 ℃ for 10 hours by adding 0.1 g of a catalyst, and the product was analyzed by gas chromatography, and as a result, the conversion of styrene reached 99.5% at 10 th hour and the selectivity of ethylene oxide reached 83.4%. In addition, in order to test the recycling performance of the catalyst, the reacted catalyst was filtered, washed thoroughly with hot water and acetone, and then dried under vacuum at 120 ℃ for 24 hours for recycling test, and it was found that the activity and selectivity of the catalyst did not decrease significantly in five cycles.
Comparative example 1
6 mmol of magnesium nitrate hexahydrate was weighed and dissolved in 50 ml of deionized water, and magnesium oxide was prepared as a catalyst under the same other reaction conditions as in example 1. Fig. 1 contains an XRD pattern of the MgO catalyst prepared in inventive comparative example 1. Fig. 3 is an SEM image of the MgO catalyst according to inventive comparative example 1.
The catalytic performance test was performed under the same other reaction conditions as in example 1, and the results showed that: the styrene conversion was 27.4% and the styrene oxide selectivity was 69.2%.
Comparative example 2
6 mmol of cobalt nitrate hexahydrate was weighed and dissolved in 50 ml of deionized water, and tricobalt tetroxide was prepared as a catalyst under the same other reaction conditions as in example 1, and FIG. 1 contains Co prepared in comparative example 2 of the invention3O4XRD pattern of catalyst. FIG. 4 shows Co prepared in comparative example 2 of the invention3O4SEM image of catalyst.
The catalytic performance test was performed under the same other reaction conditions as in example 1, and the results showed that: the styrene conversion was 61.3% and the styrene oxide selectivity was 55.6%.
Comparative example 3
Example 1 was repeated except that the calcination temperature used for the catalyst preparation was 600 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 53.2% and the selectivity to styrene oxide was 84.2%.
Example 2
Example 1 was repeated, except that 0.05 g of MgCo was added2O4And (3) adding a catalyst into a catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 78.1% and the selectivity to styrene oxide was 86.8%.
Example 3
Example 1 was repeated, except that0.15 g of MgCo2O4And (3) adding a catalyst into a catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 99.5% and the selectivity to styrene oxide was 80.5%.
Example 4
Example 1 was repeated, except that 0.20 g of MgCo was added2O4And (3) adding a catalyst into a catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 97.3% and the selectivity to styrene oxide was 78.2%.
Comparative example 4
Example 1 was repeated, except that 0.02 g of MgCo was added2O4And (3) adding a catalyst into a catalytic reaction system. Under otherwise identical reaction conditions, the conversion of styrene was 34.8% and the selectivity to styrene oxide was 80.3%.
Example 5
Example 1 was repeated except that the catalytic reaction temperature was 70 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 43.6% and the selectivity to styrene oxide was 66.9%.
Example 6
Example 1 was repeated except that the catalytic reaction temperature was 90 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 99.7% and the selectivity to styrene oxide was 78.1%.
Comparative example 5
Example 1 was repeated except that the catalytic reaction temperature was 60 ℃. Under otherwise identical reaction conditions, the conversion of styrene was 24.2% and the selectivity to styrene oxide was 43.0%.
Example 7
Example 1 was repeated, except that the catalytic reaction time was 7 h. Under otherwise identical reaction conditions, the conversion of styrene was 68.0% and the selectivity to styrene oxide was 83.8%.
Example 8
Example 1 was repeated, except that the catalytic reaction time was 8 h. Under otherwise identical reaction conditions, the conversion of styrene was 79.9% and the selectivity to styrene oxide was 83.7%.
Example 9
Example 1 was repeated, except that the catalytic reaction time was 9 h. Under otherwise identical reaction conditions, the conversion of styrene was 91.8% and the selectivity to styrene oxide was 83.5%.
Comparative example 6
Example 1 was repeated, except that the catalytic reaction time was 6 h. Under otherwise identical reaction conditions, the conversion of styrene was 59.0% and the selectivity to styrene oxide was 83.9%.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The application of magnesium cobaltate catalyst in selective oxidation reaction of styrene.
2. The use according to claim 1, characterized in that the reaction process is: styrene, tert-butyl hydroperoxide and solvent are evenly mixed, magnesium cobaltate catalyst is added, and the product of styrene oxide is obtained after reaction.
3. Use according to claim 2, characterized in that the solvent is acetonitrile.
4. Use according to claim 2, wherein the magnesium cobaltate catalyst is present in an amount of 3.2 to 12.8wt.% of styrene.
5. The use according to claim 2, wherein the mass ratio of styrene, tert-butyl hydroperoxide and solvent is 1:4: 18.8.
6. Use according to claim 2, wherein the reaction temperature is 70 to 90 ℃.
7. The use according to claim 2, wherein the reaction time is 7 to 10 hours.
8. Use according to any one of claims 1 to 7, wherein the magnesium cobaltate catalyst is prepared by a process comprising: weighing magnesium nitrate hexahydrate and cobalt nitrate hexahydrate, dissolving in deionized water, adding urea into the solution, stirring, transferring the solution into a hydrothermal kettle, keeping the temperature at 120 ℃ and 200 ℃ for 6-18 h, cooling to room temperature, filtering, washing with deionized water and ethanol, drying, and calcining to obtain the magnesium cobaltate catalyst.
9. The use according to claim 2, wherein the mass ratio of the magnesium nitrate hexahydrate, the cobalt nitrate hexahydrate and the urea is 1:2.23: 2.34.
10. Use according to claim 2, wherein the drying temperature is 50-120 ℃ and the drying time is 6-18 h; the calcination temperature is 400-600 ℃, and the calcination time is 1-4 h.
CN202110600733.9A 2021-05-31 2021-05-31 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene Active CN113387908B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110600733.9A CN113387908B (en) 2021-05-31 2021-05-31 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110600733.9A CN113387908B (en) 2021-05-31 2021-05-31 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene

Publications (2)

Publication Number Publication Date
CN113387908A true CN113387908A (en) 2021-09-14
CN113387908B CN113387908B (en) 2023-02-03

Family

ID=77619676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110600733.9A Active CN113387908B (en) 2021-05-31 2021-05-31 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene

Country Status (1)

Country Link
CN (1) CN113387908B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114733511A (en) * 2022-05-23 2022-07-12 扬州大学 V2O5/FeVO4Application of catalyst in cyclooctene epoxidation reaction
CN114890966A (en) * 2022-04-28 2022-08-12 扬州大学 Catalyst for limonene epoxidation reaction
CN115069250A (en) * 2022-07-26 2022-09-20 扬州大学 Catalyst for directly synthesizing alpha-methoxyphenylacetic acid by series catalysis of styrene and methanol and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557554A (en) * 2004-01-13 2004-12-29 厦门大学 Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method
CN101463020A (en) * 2007-12-18 2009-06-24 中国科学院兰州化学物理研究所 Method for synthesizing epoxy styrene by direct oxidation of phenylethylene
CN101979137A (en) * 2010-09-17 2011-02-23 浙江大学 Catalyst for styrene epoxidation and preparation method thereof
CN108393095A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of modified oxidized Co catalysts and its application in selectivity of styrene oxidation
CN109180608A (en) * 2018-10-16 2019-01-11 厦门大学 A kind of method of epoxidation of styrene Styryl oxide
CN109939693A (en) * 2019-03-29 2019-06-28 扬州大学 CoMn2O4Bi-metal oxide catalyst, preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1557554A (en) * 2004-01-13 2004-12-29 厦门大学 Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method
CN101463020A (en) * 2007-12-18 2009-06-24 中国科学院兰州化学物理研究所 Method for synthesizing epoxy styrene by direct oxidation of phenylethylene
CN101979137A (en) * 2010-09-17 2011-02-23 浙江大学 Catalyst for styrene epoxidation and preparation method thereof
CN108393095A (en) * 2017-02-08 2018-08-14 中国石化扬子石油化工有限公司 A kind of modified oxidized Co catalysts and its application in selectivity of styrene oxidation
CN109180608A (en) * 2018-10-16 2019-01-11 厦门大学 A kind of method of epoxidation of styrene Styryl oxide
CN109939693A (en) * 2019-03-29 2019-06-28 扬州大学 CoMn2O4Bi-metal oxide catalyst, preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘江永 等: "富含氧空位的多级0D/2D Co_3O_4催化剂在苯乙烯环氧化反应中的应用（英文）", 《催化学报》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890966A (en) * 2022-04-28 2022-08-12 扬州大学 Catalyst for limonene epoxidation reaction
CN114890966B (en) * 2022-04-28 2024-04-16 扬州大学 Catalyst for limonene epoxidation reaction
CN114733511A (en) * 2022-05-23 2022-07-12 扬州大学 V2O5/FeVO4Application of catalyst in cyclooctene epoxidation reaction
CN114733511B (en) * 2022-05-23 2023-04-14 扬州大学 V 2 O 5 /FeVO 4 Application of catalyst in cyclooctene epoxidation reaction
CN115069250A (en) * 2022-07-26 2022-09-20 扬州大学 Catalyst for directly synthesizing alpha-methoxyphenylacetic acid by series catalysis of styrene and methanol and preparation method thereof
CN115069250B (en) * 2022-07-26 2023-04-25 扬州大学 Catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and preparation method thereof

Also Published As

Publication number Publication date
CN113387908B (en) 2023-02-03

Similar Documents

Publication Publication Date Title
CN113387908B (en) Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene
CN111377890B (en) Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural
CN111604055B (en) Catalyst for preparing acetophenone by oxidizing ethylbenzene and preparation method thereof
CN108559101A (en) Method for preparing two-dimensional sheet Cu-MOF material
CN113976155A (en) Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation
CN101439882B (en) Method for synthesizing mesoporous ammonium nickel molybdate by using urea as precipitating agent
CN112337460A (en) Method for preparing Mn-based spinel low-temperature denitration catalyst by using complex acid solution
CN111116934A (en) Preparation of MOFs derivative with hollow structure and application of MOFs derivative in catalyzing olefin epoxidation
CN111533634A (en) Method for preparing propylene by directly dehydrogenating propane under low-temperature high-efficiency catalysis
CN114849789B (en) Preparation method and application of MIL-125 supported 1T-phase molybdenum sulfide composite photocatalyst
CN110898835A (en) Catalyst for efficiently treating ammonia nitrogen wastewater and preparation method thereof
CN112569945B (en) Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof
CN112517021B (en) Cobalt-doped modified tin dioxide catalyst, preparation method and application thereof
CN107376988A (en) A kind of propylene gas-phase epoxidation catalyst of high activity and its preparation method and application
CN114042448A (en) Preparation method and application of Mn-MOF-based two-dimensional sheet manganese oxide/mesoporous carbon catalyst
CN111974409A (en) Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof
CN107115895A (en) A kind of preparation method of copper-zinc-based catalyst
CN111909116A (en) Method for synthesizing N-methylmorpholine oxide by catalytic oxidation
CN115845858B (en) High-entropy oxide and high-entropy alloy catalyst, and preparation method and application thereof
CN114890966B (en) Catalyst for limonene epoxidation reaction
CN116328752B (en) Catalyst, preparation method and application of catalyst in preparation of propylene carbonate
CN114733511B (en) V 2 O 5 /FeVO 4 Application of catalyst in cyclooctene epoxidation reaction
CN107081174A (en) A kind of preparation method of needle-like copper-based catalysts
CN116371417B (en) Catalyst for synthesizing 3, 4-dimethyl pyrrole and preparation method and application thereof
CN114477298B (en) Composite oxide and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant