CN115007156A - Calcium-cobalt composite oxide catalyst, preparation method and application - Google Patents
Calcium-cobalt composite oxide catalyst, preparation method and application Download PDFInfo
- Publication number
- CN115007156A CN115007156A CN202210661175.1A CN202210661175A CN115007156A CN 115007156 A CN115007156 A CN 115007156A CN 202210661175 A CN202210661175 A CN 202210661175A CN 115007156 A CN115007156 A CN 115007156A
- Authority
- CN
- China
- Prior art keywords
- calcium
- cobalt composite
- composite oxide
- preparation
- ethylbenzene
- 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
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C07C45/36—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 compounds containing six-membered aromatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of organic reaction catalysts, and discloses a calcium-cobalt composite oxide catalyst, a preparation method and application thereof. The calcium-cobalt composite oxide catalyst consists of Co 3 O 4 、CaCo 2 O 4 、Ca 9 Co 12 O 28 The three metal oxides are prepared by a simple solvothermal method in one step. The prepared catalyst is used in the reaction of preparing acetophenone by selective oxidation of ethylbenzene, realizes high reaction activity and acetophenone selectivity, and has good stability. The catalyst disclosed by the invention is low in preparation cost, simple in preparation process and good in reaction effect, and the related catalytic reaction system only takes molecular oxygen as a unique oxygen source, does not add an activating agent, does not relate to the use of a solvent, and meets the requirements of green chemical industry and sustainable development.
Description
Technical Field
The invention relates to a calcium-cobalt composite oxide catalyst, a preparation method and application thereof in preparing acetophenone by selective oxidation of ethylbenzene, belonging to the technical field of preparation of organic reaction catalysts.
Background
Acetophenone is a colorless or yellowish viscous liquid, which is widely used as an important chemical intermediate for the synthesis of fine chemicals such as perfumes, medicines and soaps. The traditional production method is that benzene is reacted with acetyl chloride, acetic anhydride or acetic acid through Friedel-Crafts reaction in the presence of Lewis acid such as aluminum trioxide, and the like, the reaction effect is poor, the equipment corrosion is serious, and a large amount of toxic waste is generated.
In recent years, the direct catalytic oxidation of ethylbenzene to produce acetophenone has received extensive attention and research. Compared with a homogeneous catalyst, the heterogeneous catalyst has the advantage that the catalyst is easy to separate and recycle, and has industrial application prospect. On the other hand, although various oxidants can be used for the selective oxidation reaction of the ethylbenzene, the molecular oxygen has the most scale application prospect due to low price, easy obtaining and environmental protection. However, molecular oxygen is difficult to activate, and the selective oxidation reaction of ethylbenzene with molecular oxygen as an oxidant still has great challenges. Patent CN113813993A discloses Ag 2 C 2 O 4 /Ag 2 The preparation of the O composite catalyst and the application thereof in the ethylbenzene oxidation, but the preparation of the catalyst needs noble metal Ag and the preparation process is complex. The prepared catalyst with low price, simple preparation method and excellent reaction effect is a difficult point and a breakthrough point in the field of ethylbenzene molecular oxygen selective oxidation.
Disclosure of Invention
The invention aims to provide a catalyst for preparing acetophenone by selective oxidation of ethylbenzene and a preparation method thereof.
A calcium cobalt composite oxide catalyst comprises Co 3 O 4 、CaCo 2 O 4 、Ca 9 Co 12 O 28 Three metal oxides, wherein the molar ratio of Ca to Co is 1: 5-1: 1; the calcium-cobalt composite oxide catalyst consists of Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea, polyvinylpyrrolidone and sodium citrateThe solvent is dried and roasted after thermal reaction to prepare the catalyst.
The invention also provides a preparation method of the calcium-cobalt composite oxide catalyst, which comprises the following steps:
mixing Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 Dissolving O, urea, polyvinylpyrrolidone and sodium citrate in a mixed solution of deionized water and ethanol, stirring, placing the solution in a hydrothermal kettle, reacting at 180-200 ℃ for 12-20 h, naturally cooling the hydrothermal kettle to room temperature, performing suction filtration, and washing with deionized water for several times; and drying the obtained product, and roasting the dried product in the air at 550-850 ℃ for 1-3 h to obtain the calcium-cobalt composite oxide catalyst.
Further, Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 The mass ratio of the O to the urea to the polyvinylpyrrolidone to the sodium citrate is 1: 3.5-6.5: 3.1:8.5: 4.4.
And further, drying the washed product at 75-85 ℃ for 12-24 h.
Further, the stirring time is 1-3 h.
Further, the volume ratio of the deionized water to the ethanol is 1: 1-5: 1.
Further, the preparation process of the calcium-cobalt composite oxide catalyst comprises the following steps:
(1) mixing Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 Dissolving O, urea, polyvinylpyrrolidone and sodium citrate in the mixed solution of deionized water and ethanol, and stirring for 1-3 h.
(2) And (3) placing the solution in a hydrothermal kettle, reacting at 180 ℃ for 12-20 h, naturally cooling the hydrothermal kettle to room temperature, performing suction filtration, and washing with deionized water for several times.
(3) And drying the obtained product at 80 ℃ for 12-24 h, and then roasting in air at 800 ℃ for 1-3 h.
Further, Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 Substances of O, urea, polyvinylpyrrolidone and sodium citrateThe quantity ratio is 1: 3.5-6.5: 3.1:8.5: 4.4.
the invention also provides application of the calcium-cobalt composite oxide catalyst in preparing acetophenone by selective oxidation of ethylbenzene.
The reaction process is as follows: adding a calcium-cobalt composite oxide catalyst and ethylbenzene into a high-pressure reaction kettle, and reacting for a period of time at a certain temperature and pressure by taking molecular oxygen as an oxidant to obtain the acetophenone.
Furthermore, the dosage of the catalyst is 0.0025-0.006 g/mL based on the volume of the ethylbenzene,
further, the reaction temperature is 110-140 ℃, the reaction time is 2-8 h, and the reaction pressure is 0.4-1.0 MPa.
Compared with the prior art, the invention has the following advantages:
(1) the calcium-cobalt composite oxide catalyst has low preparation cost and simple preparation process;
(2) the catalyst is used for preparing acetophenone by selective oxidation of ethylbenzene, only uses molecular oxygen as a unique oxygen source, does not add an activating agent, does not relate to the use of a solvent, meets the requirements of green chemical industry and sustainable development, has good reaction effect, does not obviously reduce the catalytic effect after repeated use for many times, and has good industrial application prospect.
Drawings
FIG. 1 shows a Ca-Co composite oxide catalyst prepared in inventive example 1 and Co in comparative example 1 3 O 4 And XRD pattern of CaO in comparative example 2.
Fig. 2 is an SEM image of the calcium cobalt composite oxide catalyst prepared in inventive example 1.
Fig. 3 is a TEM image of the calcium cobalt composite oxide catalyst prepared in inventive example 1.
Fig. 4 is an HRTEM image of the calcium cobalt composite oxide catalyst prepared in inventive example 1.
Detailed Description
The technical solution of the present invention is explained in detail below with reference to the accompanying drawings and examples.
Example 1
Adding 1mmol Ca (NO) 3 ) 2 ·4H 2 O，4mmol Co(NO 3 ) 2 ·6H 2 O, 4mmol of sodium citrate, 12mmol of urea and 2g of polyvinylpyrrolidone are dissolved in a mixed solution of 30mL of ethanol and 30mL of deionized water, and stirred for 1 h. And then, placing the solution in a hydrothermal kettle, reacting for 12 hours at 180 ℃, filtering after the hydrothermal kettle is naturally cooled to room temperature, and washing for a plurality of times by using deionized water. Drying the obtained product at 80 deg.C for 12h, and calcining at 800 deg.C in air for 1h to obtain calcium-cobalt composite oxide catalyst (labeled as Ca) x Co y O z )。
The prepared catalyst is used for the selective oxidation reaction of ethylbenzene. 0.1g of Ca x Co y O z The catalyst and 20mL of ethylbenzene were added to the autoclave. The molecular oxygen is used as an oxidant, the reaction is carried out for 6 hours at the temperature of 130 ℃ and under the pressure of 0.8MPa, and the obtained product is analyzed by gas chromatography, so that the conversion rate of ethylbenzene reaches 74.3 percent, and the selectivity of acetophenone reaches 93.6 percent. In addition, to test the catalyst for recycling performance, the reacted catalyst was filtered off and washed thoroughly with hot deionized water and acetone, and then dried at 100 ℃ for 24 hours before being used for the next test. As a result, it was found that Ca x Co y O z After the catalyst is recycled for five times, the catalytic activity and the selectivity are not obviously reduced.
Comparative example 1
The preparation is identical to example 1, with the only difference that the metal source does not involve Co, only 5mmol of Ca (NO) are added 3 ) 2 ·4H 2 O, and the obtained catalyst is a CaO catalyst. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 18.8% and the acetophenone selectivity was 66.1%.
The XRD pattern of the prepared CaO catalyst is included in fig. 1.
Comparative example 2
The preparation is identical to example 1, with the only difference that the metal source does not involve Ca, only 5mmol of Co (NO) are added 3 ) 2 ·6H 2 O, the catalyst obtained is Co 3 O 4 A catalyst. The catalytic performance test was carried out under the same conditions as in example 1, and the results were remarkableThe following steps: the ethylbenzene conversion was 47.3% and the acetophenone selectivity was 79.7%.
FIG. 1 contains prepared Co 3 O 4 XRD pattern of the catalyst.
Comparative example 3
The preparation is identical to example 1, the only difference being Ca (NO) 3 ) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1: 1. the catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 37.1% and the acetophenone selectivity was 76.4%.
Comparative example 4
The preparation is identical to example 1, the only difference being Ca (NO) 3 ) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1: 2. the catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 52.6% and the acetophenone selectivity was 84.9%.
Comparative example 5
The preparation is identical to example 1, the only difference being Ca (NO) 3 ) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:3. the catalytic performance test was performed in the same manner as in example 1, and the results showed that: the conversion of ethylbenzene was 16.8% and the selectivity to acetophenone was 61.6%.
Comparative example 6
The preparation is identical to example 1, the only difference being Ca (NO) 3 ) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1: 5. the catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 44.3% and the acetophenone selectivity was 75.8%.
Comparative example 7
The preparation was identical to example 1, with the only difference that the amount of urea was increased to 1.2 g. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 61.4% and the acetophenone selectivity was 89.5%.
Comparative example 8
The preparation was carried out in the same manner as in example 1, except that the amount of polyvinylpyrrolidone was reduced to 1 g. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 46.7% and the acetophenone selectivity was 79.7%.
Comparative example 9
The preparation was identical to example 1, with the only difference that no sodium citrate was added. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the conversion of ethylbenzene was 42.7% and the selectivity to acetophenone was 70.8%.
Comparative example 10
The preparation method was the same as in example 1, except that the calcination temperature was changed to 600 ℃. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the ethylbenzene conversion was 41.9% and the acetophenone selectivity was 73.3%.
Comparative example 11
The preparation was carried out in the same manner as in example 1, except that the calcination temperature was changed to 700 ℃. The catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the conversion of ethylbenzene was 66.5% and the selectivity to acetophenone was 89.6%.
Comparative example 12
The preparation was the same as in example 1, except that the ratio of deionized water to ethanol was 5: 1. the catalytic performance test was performed in the same manner as in example 1, and the results showed that: the ethylbenzene conversion was 37.1% and the acetophenone selectivity was 62.8%.
Comparative example 13
The preparation was the same as in example 1, except that the ratio of deionized water to ethanol was 2: 1. the catalytic performance test was performed under the same conditions as in example 1, and the results showed that: the conversion of ethylbenzene was 54.2% and the selectivity to acetophenone was 85.0%.
Example 2
Example 1 was repeated, except that 0.05g of Ca was added x Co y O z The catalyst is put into a reaction kettle. At itUnder the same reaction conditions, the conversion rate of the ethylbenzene was 57.8%, and the selectivity of the acetophenone was 87.0%.
Example 3
Example 1 was repeated, except that 0.08g of Ca was added x Co y O z The catalyst is put into a reaction kettle. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 70.3% and the selectivity to acetophenone was 93.0%.
Example 4
Example 1 was repeated, except that 0.12g of Ca was added x Co y O z The catalyst is put into a reaction kettle. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 63.8% and the selectivity to acetophenone was 88.1%.
Example 5
Example 1 was repeated except that the ethylbenzene oxidation reaction temperature was 110 ℃. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 47.5% and the selectivity to acetophenone was 81.3%.
Example 6
Example 1 was repeated except that the ethylbenzene oxidation reaction temperature was 120 ℃. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 56.9% and the selectivity to acetophenone was 84.7%.
Example 7
Example 1 was repeated except that the ethylbenzene oxidation reaction temperature was 140 ℃. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 43.6% and the selectivity to acetophenone was 77.3%.
Example 8
Example 1 was repeated, except that the reaction time was 2 h. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 30.7% and the selectivity to acetophenone was 76.3%.
Example 9
Example 1 was repeated, except that the reaction time was 4 h. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 54.5% and the selectivity to acetophenone was 86.4%.
Example 10
Example 1 was repeated, except that the reaction time was 8 h. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 77.2% and the selectivity to acetophenone was 90.0%.
Example 11
Example 1 was repeated except that the ethylbenzene oxidation reaction pressure was 0.4 MPa. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 20.6% and the selectivity to acetophenone was 64.5%.
Example 12
Example 1 was repeated except that the ethylbenzene oxidation reaction pressure was 0.6 MPa. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 33.4% and the selectivity to acetophenone was 68.3%.
Example 13
Example 1 was repeated except that the ethylbenzene oxidation reaction pressure was 1.0 MPa. Under otherwise identical reaction conditions, the conversion of ethylbenzene was 74.6% and the selectivity to acetophenone was 91.4%.
The experimental results show that the calcium-cobalt composite oxide catalyst has excellent reaction effects including high reaction activity, product selectivity, stability and the like in the catalytic ethylbenzene molecular oxygen selective oxidation reaction, and is remarkably superior to the corresponding single metal oxide catalyst. The calcium-cobalt composite oxide has rich heterogeneous interfaces with strong interaction, is beneficial to the generation of weakened interface Co-O bonds, induces the generation of more oxygen vacancies, improves the activity of lattice oxygen, and finally promotes the activation of molecular oxygen and the generation of active superoxide radical. The invention provides a novel catalyst design strategy for improving the oxidation performance of molecular oxygen of ethylbenzene.
It will be readily appreciated by those skilled in the art that the above-described embodiments are merely illustrative of the present invention and are not intended to limit the present invention, and any extension, modification, replacement, improvement, etc. made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. Calcium-cobalt composite oxygenA catalyst compound, the calcium cobalt composite oxide catalyst comprising Co 3 O 4 、CaCo 2 O 4 、Ca 9 Co 12 O 28 Three metal oxides, wherein the molar ratio of Ca to Co is 1: 1-1: 5; the calcium-cobalt composite oxide catalyst consists of Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 The material is prepared by carrying out thermal reaction on O, urea, polyvinylpyrrolidone and sodium citrate with a solvent, and then drying and roasting.
2. The method for producing a calcium-cobalt composite oxide catalyst according to claim 1, characterized by comprising the steps of:
mixing Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 Dissolving O, urea, polyvinylpyrrolidone and sodium citrate in a mixed solution of deionized water and ethanol, stirring, placing the solution in a hydrothermal kettle, reacting at 180-200 ℃ for 12-20 h, naturally cooling the hydrothermal kettle to room temperature, performing suction filtration, and washing with deionized water for several times; and drying the obtained product, and roasting the dried product in the air at 550-850 ℃ for 1-3 h to obtain the calcium-cobalt composite oxide catalyst.
3. The method according to claim 2, wherein Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 The mass ratio of the O to the urea to the polyvinylpyrrolidone to the sodium citrate is 1: 3.5-6.5: 3.1:8.5: 4.4.
4. The preparation method according to claim 2, wherein the washed product is dried at 75-85 ℃ for 12-24 hours.
5. The preparation method according to claim 2, wherein the stirring time is 1 to 3 hours.
6. The preparation method of claim 2, wherein the volume ratio of the deionized water to the ethanol is 1:1 to 5: 1.
7. The use of the calcium-cobalt composite oxide catalyst of claim 1 in the selective oxidation of ethylbenzene to acetophenone.
8. The application of claim 7, wherein the calcium-cobalt composite oxide catalyst and the ethylbenzene are added into a high-pressure reaction kettle, and the acetophenone is prepared by taking molecular oxygen as an oxidant.
9. The use according to claim 8, wherein the amount of catalyst is 0.0025 to 0.006g/mL based on the volume of ethylbenzene.
10. The method of claim 8, wherein the reaction temperature is 110-140 ℃, the reaction time is 2-8 h, and the reaction pressure is 0.4-1.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210661175.1A CN115007156B (en) | 2022-06-13 | 2022-06-13 | Calcium-cobalt composite oxide catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210661175.1A CN115007156B (en) | 2022-06-13 | 2022-06-13 | Calcium-cobalt composite oxide catalyst, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115007156A true CN115007156A (en) | 2022-09-06 |
| CN115007156B CN115007156B (en) | 2023-07-25 |
Family
ID=83075286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210661175.1A Active CN115007156B (en) | 2022-06-13 | 2022-06-13 | Calcium-cobalt composite oxide catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115007156B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110833844A (en) * | 2019-10-28 | 2020-02-25 | 扬州大学 | Application of cobalt carbonate in preparation of acetophenone by molecular oxygen solvent-free catalytic oxidation of ethylbenzene |
-
2022
- 2022-06-13 CN CN202210661175.1A patent/CN115007156B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110833844A (en) * | 2019-10-28 | 2020-02-25 | 扬州大学 | Application of cobalt carbonate in preparation of acetophenone by molecular oxygen solvent-free catalytic oxidation of ethylbenzene |
Non-Patent Citations (1)
| Title |
|---|
| LINLIN LI ET AL.,: "Controlled synthesis of porous CaCo2O4 nanoflowers and their multifunctional applications for lithium ion batteries and oxygen evolution reaction" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115007156B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6304830B2 (en) | Catalyst for butadiene production by oxidative dehydrogenation of butene used in fluidized bed reactor, and production method and use thereof | |
| WO2014173229A1 (en) | Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof | |
| CN111604055B (en) | Catalyst for preparing acetophenone by oxidizing ethylbenzene and preparation method thereof | |
| CN111960948B (en) | Synthesis process of tetrabutylammonium bromide | |
| CN110052271B (en) | Graphene-coated nickel-nickel oxide catalyst and application thereof in preparation of lactic acid | |
| CN109939693B (en) | CoMn2O4Bimetallic oxide catalyst, preparation method and application | |
| CN113387908B (en) | Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene | |
| CN107572585B (en) | A kind of bismuth oxybromide visible light catalyst and preparation method thereof | |
| WO2020192477A1 (en) | Catalyst and method for preparing isopentyl diol | |
| CN112920041B (en) | Method for preparing hydroxy dibasic acid by catalyzing acetyl acid raw material to oxidize | |
| CN111747831B (en) | Method for preparing cyclopentanone | |
| CN105854859A (en) | Efficient bifunctional catalyst as well as preparation and application thereof | |
| CN111170829B (en) | Preparation method of hexamethyl indanol | |
| CN105440005A (en) | Method for preparation of epsilon-caprolactone by catalysis of cyclohexanone by MgO / Fe2O3 | |
| CN115007156A (en) | Calcium-cobalt composite oxide catalyst, preparation method and application | |
| CN111389445A (en) | Composite solid acid catalyst for preparing 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and preparation method thereof | |
| CN108069838A (en) | A kind of method that photochemical catalytic oxidation ethylene glycol prepares formaldehyde | |
| CN114950518B (en) | Cobalt/tubular graphite phase carbon nitride composite material and preparation method and application thereof | |
| CN106925259A (en) | FCC Off-Gas over Zeolite Catalyst propylene hydration prepares catalyst of isopropanol and its preparation method and application | |
| CN106905266B (en) | A kind of method that epoxidation of styrene prepares Styryl oxide | |
| CN112569945B (en) | Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof | |
| CN108855158A (en) | A kind of preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN108503518A (en) | A kind of preparation and its application of compound sepiolite base catalyst | |
| CN104549413B (en) | Nanogold catalyst for preparing phenol through direct hydroxylation of benzene as well as preparation method and application of nanogold catalyst |
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 |