CN115007156B - Calcium-cobalt composite oxide catalyst, preparation method and application - Google Patents
Calcium-cobalt composite oxide catalyst, preparation method and application Download PDFInfo
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- CN115007156B CN115007156B CN202210661175.1A CN202210661175A CN115007156B CN 115007156 B CN115007156 B CN 115007156B CN 202210661175 A CN202210661175 A CN 202210661175A CN 115007156 B CN115007156 B CN 115007156B
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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
- B01J23/78—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
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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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- 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
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- 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
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- 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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of organic reaction catalyst preparationDiscloses a calcium-cobalt composite oxide catalyst, a preparation method and application thereof. The calcium-cobalt composite oxide catalyst is prepared from Co 3 O 4 、CaCo 2 O 4 、Ca 9 Co 12 O 28 Three metal oxides are prepared in one step by a simple solvothermal method. The catalyst is used in the reaction of preparing acetophenone by ethylbenzene selective oxidation, realizes high reaction activity and acetophenone selectivity, and has good stability. The catalyst has the advantages of low preparation cost, simple preparation process and good reaction effect, and the related catalytic reaction system only uses molecular oxygen as a unique oxygen source, does not add an activating agent, does not involve 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 ethylbenzene selective oxidation, and belongs to the technical field of preparation of organic reaction catalysts.
Background
Acetophenone is a colorless or pale yellow viscous liquid, and 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 reacts with acetyl chloride, acetic anhydride or acetic acid through Friedel-Crafts reaction in the presence of Lewis acid such as aluminum oxide, etc., the reaction effect is poor, 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 advantages of easy separation and recycling of the catalyst, and has more industrial application prospect. On the other hand, although various oxidants can be used for the selective oxidation reaction of ethylbenzene, molecular oxygen has the best large-scale application prospect due to low cost, easy availability and environmental friendliness. However, molecular oxygen is difficult to activate, and ethylbenzene selective oxidation reactions using molecular oxygen as an oxidant remain very challenging. Patent CN113813993a discloses Ag 2 C 2 O 4 /Ag 2 Preparation of O composite catalyst and application thereof in ethylbenzene oxidation, but preparation of the catalyst requires noble metal Ag and preparationThe process is complicated. The catalyst which is low in cost, simple in preparation method and excellent in 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 ethylbenzene selective oxidation and a preparation method thereof, wherein molecular oxygen is only used as a sole oxygen source, an activating agent is not added, the reaction effect of a solvent is good, and the catalytic effect is not obviously reduced after repeated use for many times.
A 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 1:5-1:1; 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 citrate are subjected to solvothermal reaction and then are dried and roasted to prepare the modified polyvinyl pyrrolidone.
The invention also provides a preparation method of the calcium-cobalt composite oxide catalyst, which comprises the following steps:
ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea, polyvinylpyrrolidone and sodium citrate are dissolved in a mixed solution of deionized water and ethanol, the mixed solution is stirred and then placed in a hydrothermal kettle for reaction for 12-20 hours at 180-200 ℃, and after the hydrothermal kettle is naturally cooled to room temperature, the solution is filtered and washed with deionized water for several times; and drying the obtained product, and roasting in 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 O, urea, polyvinylpyrrolidone and sodium citrate is 1:3.5-6.5:3.1:8.5:4.4.
Further, the washed product is dried for 12 to 24 hours at the temperature of 75 to 85 ℃.
Further, the stirring time is 1-3 h.
Further, the volume ratio of deionized water to ethanol is 1:1-5:1.
Further, the preparation process of the calcium-cobalt composite oxide catalyst comprises the following steps:
(1) Ca (NO) 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea, polyvinylpyrrolidone and sodium citrate are dissolved in the mixed solution of deionized water and ethanol and stirred for 1-3 h.
(2) The solution is placed in a hydrothermal kettle to react for 12-20 hours at 180 ℃, and after the hydrothermal kettle is naturally cooled to room temperature, the solution is filtered and washed with deionized water for several times.
(3) The obtained product is dried for 12 to 24 hours at 80 ℃, and then baked for 1 to 3 hours at 800 ℃ in air.
Further, ca (NO 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 The mass ratio of O, urea, polyvinylpyrrolidone and sodium citrate is 1:3.5 to 6.5:3.1:8.5:4.4.
the invention also provides application of the calcium-cobalt composite oxide catalyst in preparing acetophenone by ethylbenzene selective oxidation.
The reaction process is as follows: adding a calcium-cobalt composite oxide catalyst and ethylbenzene into a high-pressure reaction kettle, taking molecular oxygen as an oxidant, and reacting for a period of time at a certain temperature and under a certain pressure to obtain acetophenone.
Further, the catalyst is used in an amount of 0.0025 to 0.006g/mL based on the volume of 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 preparation cost of the calcium-cobalt composite oxide catalyst is low, and the preparation process is simple;
(2) The catalyst is used for preparing acetophenone by selective oxidation of ethylbenzene, only molecular oxygen is used as a sole oxygen source, no activator is added, no solvent is used, the requirements of green chemical industry and sustainable development are met, the reaction effect is good, the catalytic effect is not obviously reduced after repeated use for many times, and the catalyst has good industrial application prospect.
Drawings
FIG. 1 shows a calcium-cobalt composite oxide catalyst prepared in inventive example 1 and Co in comparative example 1 3 O 4 And the 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 scheme of the invention is described in detail below with reference to the accompanying drawings and examples.
Example 1
1mmol of Ca (NO) 3 ) 2 ·4H 2 O，4mmol Co(NO 3 ) 2 ·6H 2 O,4mmol sodium citrate, 12mmol urea and 2g polyvinylpyrrolidone were dissolved in a mixed solution of 30mL ethanol and 30mL deionized water and stirred for 1h. Then, the solution is placed in a hydrothermal kettle to react for 12 hours at 180 ℃, and after the hydrothermal kettle is naturally cooled to room temperature, the solution is filtered by suction and washed with deionized water for several times. The obtained product was dried at 80℃for 12 hours, and then calcined in air at 800℃for 1 hour to obtain a calcium-cobalt composite oxide catalyst (labeled Ca x Co y O z )。
The catalyst is used for the selective oxidation reaction of ethylbenzene. 0.1g of Ca x Co y O z Catalyst and 20mL of ethylbenzene were added to the autoclave. Molecular oxygen is used as an oxidant, the reaction is carried out for 6 hours at 130 ℃ and 0.8MPa, and the obtained product is analyzed by gas chromatography, so that the conversion rate of ethylbenzene reaches 74.3%, and the selectivity of acetophenone reaches 93.6%. In addition, in order to test the recycling performance of the catalyst, the reacted catalyst was filtered out and washed with hot deionized water and acetone sufficiently, and then dried at 100℃for 24 hours for the next timeAnd (5) testing. 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 was the same as in example 1, except that the metal source was Co-free and only 5mmol Ca (NO 3 ) 2 ·4H 2 O, the catalyst is CaO catalyst. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 18.8% and the acetophenone selectivity was 66.1%.
The XRD pattern of the prepared CaO catalyst is contained in FIG. 1.
Comparative example 2
The preparation was the same as in example 1, except that the metal source was not Ca, only 5mmol Co (NO 3 ) 2 ·6H 2 O, the catalyst obtained is Co 3 O 4 A catalyst. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 47.3% and the selectivity to acetophenone was 79.7%.
FIG. 1 contains Co produced 3 O 4 XRD pattern of the catalyst.
Comparative example 3
The preparation was the same as in example 1, except that 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 carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 37.1% and the selectivity to acetophenone was 76.4%.
Comparative example 4
The preparation was the same as in example 1, except that 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 carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 52.6% and the selectivity to acetophenone was 84.9%.
Comparative example 5
The preparation method is the same as that of example 1, but is notSame as 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 carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 16.8% and the selectivity to acetophenone was 61.6%.
Comparative example 6
The preparation was the same as in example 1, except that 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 carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 44.3% and the acetophenone selectivity was 75.8%.
Comparative example 7
The preparation was the same as in example 1, except that the amount of urea was increased to 1.2g. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 61.4% and the selectivity to acetophenone was 89.5%.
Comparative example 8
The preparation was the same as in example 1, except that the amount of polyvinylpyrrolidone was reduced to 1g. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 46.7% and the selectivity to acetophenone was 79.7%.
Comparative example 9
The preparation was the same as in example 1, except that sodium citrate was not added. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 42.7% and the acetophenone selectivity was 70.8%.
Comparative example 10
The preparation was the same as in example 1, except that the firing temperature was changed to 600 ℃. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 41.9% and the acetophenone selectivity was 73.3%.
Comparative example 11
The preparation was the same as in example 1, except that the firing temperature was changed to 700 ℃. The catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion 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 deionized water to ethanol ratio was 5:1. the catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion was 37.1% and the selectivity to acetophenone was 62.8%.
Comparative example 13
The preparation was the same as in example 1, except that the deionized water to ethanol ratio was 2:1. the catalytic performance test was carried out in the same manner as in example 1, and the result showed that: the ethylbenzene conversion 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. Under the same other reaction conditions, the conversion of ethylbenzene was 57.8% and the selectivity of 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 the same other reaction conditions, the conversion of ethylbenzene was 70.3% and the selectivity of 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 the same other reaction conditions, the conversion of ethylbenzene was 63.8% and the selectivity of acetophenone was 88.1%.
Example 5
Example 1 was repeated except that the ethylbenzene oxidation reaction temperature was 110 ℃. Under the same other 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 the same other reaction conditions, the conversion of ethylbenzene was 56.9% and the selectivity of acetophenone was 84.7%.
Example 7
Example 1 was repeated except that the ethylbenzene oxidation reaction temperature was 140 ℃. Under the same other reaction conditions, the conversion of ethylbenzene was 43.6% and the selectivity of acetophenone was 77.3%.
Example 8
Example 1 was repeated with the difference that the reaction time was 2h. 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 with the difference that the reaction time was 4h. Under the same other reaction conditions, the conversion of ethylbenzene was 54.5% and the selectivity to acetophenone was 86.4%.
Example 10
Example 1 was repeated with the difference that the reaction time was 8h. Under the same other reaction conditions, the conversion of ethylbenzene was 77.2% and the selectivity of acetophenone was 90.0%.
Example 11
Example 1 was repeated except that the ethylbenzene oxidation reaction pressure was 0.4MPa. Under the same other reaction conditions, the conversion of ethylbenzene was 20.6% and the selectivity of acetophenone was 64.5%.
Example 12
Example 1 was repeated except that the ethylbenzene oxidation reaction pressure was 0.6MPa. Under the same other 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 1.0MPa. Under the same other reaction conditions, the conversion of ethylbenzene was 74.6% and the selectivity of acetophenone was 91.4%.
The experimental results show that the calcium-cobalt composite oxide catalyst has excellent reaction effects in catalyzing ethylbenzene molecular oxygen selective oxidation reaction, including high reaction activity, product selectivity, stability and the like, and is obviously superior to the corresponding single metal oxide catalyst. The calcium-cobalt composite oxide provided by the invention has rich heterogeneous interfaces with strong interaction, is favorable for generating weakened interface Co-O bonds, induces more oxygen vacancies to generate, promotes the activity of lattice oxygen, and finally promotes the activation of molecular oxygen and the generation of active superoxide radicals. The invention provides a new strategy for designing a catalyst for improving the molecular oxygen oxidation performance of ethylbenzene.
It will be readily appreciated by those skilled in the art that the foregoing description of the embodiments has been provided for the purpose of illustration only and not for the purpose of limiting the invention, and that any such extensions, modifications, alternatives, improvements etc. that fall within the spirit and principles of the invention shall fall within the scope of the present invention.
Claims (8)
1. The application of a calcium-cobalt composite oxide catalyst in preparing acetophenone by ethylbenzene selective oxidation is characterized in that the calcium-cobalt composite oxide catalyst and ethylbenzene are added into a high-pressure reaction kettle, and molecular oxygen is used as an oxidant to prepare acetophenone, wherein the 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 1:1-1:5; 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 citrate are subjected to solvothermal reaction and then are dried and roasted to prepare the modified polyvinyl pyrrolidone.
2. The use according to claim 1, wherein the preparation method of the calcium-cobalt composite oxide catalyst comprises the following steps:
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, stirringThen placing the solution into a hydrothermal kettle, reacting for 12-20 hours at 180-200 ℃, and after the hydrothermal kettle is naturally cooled to room temperature, carrying out suction filtration and washing for a plurality of times by deionized water; and drying the obtained product, and roasting in air at 550-850 ℃ for 1-3 hours to obtain the calcium-cobalt composite oxide catalyst.
3. Use according to claim 2, characterized in that Ca (NO 3 ) 2 ·4H 2 O、Co(NO 3 ) 2 ·6H 2 The mass ratio of O, urea, polyvinylpyrrolidone and sodium citrate is 1:3.5-6.5:3.1:8.5:4.4.
4. The use according to claim 2, wherein the washed product is dried at 75-85 ℃ for 12-24 hours.
5. The use according to claim 2, wherein the stirring time is 1-3 hours.
6. The use of claim 2, wherein the volume ratio of deionized water to ethanol is 1:1 to 5:1.
7. The use according to claim 1, wherein the catalyst is used in an amount of 0.0025 to 0.006g/mL based on the volume of ethylbenzene.
8. The use according to claim 1, wherein the reaction temperature is 110-140 ℃, the reaction time is 2-8 hours, and the reaction pressure is 0.4-1.0 MPa.
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