CN110790659A - Method for preparing cyclohexanone - Google Patents
Method for preparing cyclohexanone Download PDFInfo
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- CN110790659A CN110790659A CN201911104962.0A CN201911104962A CN110790659A CN 110790659 A CN110790659 A CN 110790659A CN 201911104962 A CN201911104962 A CN 201911104962A CN 110790659 A CN110790659 A CN 110790659A
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 32
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 26
- GUWKQWHKSFBVAC-UHFFFAOYSA-N [C].[Au] Chemical compound [C].[Au] GUWKQWHKSFBVAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 14
- 238000013032 photocatalytic reaction Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 6
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960000541 cetyl alcohol Drugs 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000002256 photodeposition Methods 0.000 claims description 3
- 238000005956 quaternization reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/39—
-
- B01J35/394—
Abstract
The invention belongs to the field of organic synthesis, and particularly discloses a method for preparing cyclohexanone from cyclohexane through photocatalytic oxidation. The method uses a gold-carbon composite photocatalyst, and under the condition of visible light, the reaction substrate cyclohexane is oxidized in one step to generate cyclohexanone. The gold-carbon composite photocatalyst is prepared by a four-step method, and mainly comprises the steps of S1 precursor preparation, S2 precursor briquetting, S3 carrier preparation and S4 gold nanoparticle loading. The method for preparing cyclohexanone is prepared by a photocatalytic one-step method, visible light is used as a light source, air or oxygen is used as an oxidant, the reaction path is simple and direct, the reaction condition is mild and safe, the conversion rate of reaction substrate cyclohexane is high, and the selectivity of reaction product cyclohexanone is high.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing cyclohexanone from cyclohexane through photocatalytic oxidation.
Background
KA oil is a general name of cyclohexanol and cyclohexanone, is a key intermediate product in industrial production, and is an important chemical raw material related to the national civilization. Currently, in the industrial production of KA oil, soluble cobalt salt is used as a catalyst to catalyze the oxidation of cyclohexane under a certain temperature and oxygen pressure. To avoid over-oxidation, the conversion of cyclohexane is about 4% and the overall selectivity of cyclohexanol and cyclohexanone is 70-85%. The existing process has high energy consumption, low efficiency and great environmental hazard. In addition, the process cannot selectively generate cyclohexanol or cyclohexanone, so that certain limitations are caused to downstream production and application. Therefore, it is of great significance to explore catalytic paths with mild reaction conditions, high catalytic efficiency and good selectivity.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention provides a method for preparing cyclohexanone.
The technical scheme is as follows: in order to achieve the aim, the invention provides a method for preparing cyclohexanone, which uses a gold-carbon composite photocatalyst to oxidize a reaction substrate cyclohexane in one step to generate cyclohexanone under the condition of visible light;
the gold-carbon composite photocatalyst is prepared by the following steps:
preparation of S1 precursor: carrying out quaternization reaction on 4-cyano benzyl bromide and 4,4' -bipyridyl to generate a humate, thus obtaining a precursor;
briquetting of S2 precursor: filling the precursor into a tablet press and extruding into blocks;
preparation of S3 vector: carrying out heat treatment on the massive precursor prepared in the step S2 under the condition of air isolation to obtain a carrier;
s4 loading gold nanoparticles: and loading gold nanoparticles on the carrier by using a photo-deposition method to obtain the gold-carbon composite photocatalyst.
The method for preparing cyclohexanone is driven by visible light, and cyclohexane is oxidized to generate cyclohexanone in a high selectivity manner under mild reaction conditions by using a novel gold-carbon composite photocatalyst. The oxidant used may be either air or oxygen. The gold-carbon composite photocatalyst is prepared by a four-step method, wherein the carbon material part has strong photoresponse and generates a photo-generated carrier with oxidation reduction capability, and the supported gold nanoparticles can effectively promote the migration of the photo-generated carrier and can generate certain photoresponse.
Further, in the above method for preparing cyclohexanone, the reaction conditions for oxidizing cyclohexane to form cyclohexanone are as follows: adding acetonitrile serving as a solvent, cyclohexane serving as a reaction substrate and the gold-carbon composite photocatalyst into a quartz photocatalytic reaction tube, and reacting under the condition of visible light. And the acetonitrile solvent is selected, so that the dissolving amount of oxygen molecules is favorably improved.
Preferably, in the method for preparing cyclohexanone, a light source for visible light irradiation filters an ultraviolet band by using a 500W xenon lamp and an optical filter with a cut-off wavelength of 400 nm; the distance between the center of the xenon lamp and the center of the reaction tube is 150 mm.
Preferably, in the method for preparing cyclohexanone, the capacity of the photocatalytic reaction tube is 50mL, the dosage of the dissolved acetonitrile is 15mL, the dosage of cyclohexane is 2g, the dosage of the gold-carbon composite photocatalyst is 0.05g, and the reaction time is 6 h.
As an improvement of the invention, in the method for preparing cyclohexanone, a plug is arranged at the opening of the photocatalytic reaction tube, and a condensation reflux device is arranged on the plug; a pipeline is also arranged in the plug in a penetrating way, one end of the pipeline extends into the solution, the other end of the pipeline is connected with an oxygen source, oxygen gas flows through the pipeline to bubble into the solution, and the flow rate is 5 mL/min. Since the concentration of the reactant is high and the oxygen content in the air is low, the oxygen bubbling can promote the oxidation reaction. The condensing reflux device is added to prevent the components in the reaction tube from being taken away by the gas flow and lost.
Preferably, in the above method for preparing cyclohexanone, in step S1, the reactants 4-cyanobenzyl bromide and 4,4' -bipyridine are added into the solvent anhydrous ethanol according to the molar ratio of 2:1, the mass ratio of the solvent to the reactants is 5:1, the reaction is performed for 8 hours at 78 ℃, the mixture obtained by the reaction is washed for 3 times with ethyl acetate, and the precursor is obtained after filtering and drying.
Preferably, in the method for preparing cyclohexanone, step S2, the precursor is ground into powder, and the powder is loaded into a tablet press and pressed into a cylindrical block with a mass of 2g under a pressure of 30 MPa.
Preferably, in the method for preparing cyclohexanone, in step S3, the bulk precursor prepared in step S2 is put into a tube furnace, high-purity nitrogen is introduced at a flow rate of 120mL/min, after 20min, the temperature is raised to 520 ℃, the temperature raising rate is 5 ℃/min, the temperature is maintained for 6h, then the temperature is raised to 930 ℃, the temperature raising rate is 2 ℃/min, the temperature is maintained for 4h, then the bulk precursor is naturally cooled to room temperature, and the bulk precursor is ground into powder to obtain the carrier. And roasting the precursor by adopting a two-step stepwise heating method to prepare the carbon material with optical activity.
Preferably, the above process for producing cyclohexanone is characterized in that: in step S4, 15mL of aqueous solution of chloroauric acid with concentration of 0.5mmol/L is put into a photoreaction tube, 0.3g of palmityl alcohol is added, 1g of carrier is added, stirring is started, a 500W high-pressure mercury lamp is used for light reaction for 5 hours at normal temperature, and the gold-carbon composite photocatalyst is obtained after solid is filtered out, washed and dried. Ultraviolet light is used for light deposition, gold chloride acid provides a gold source, and a small amount of palm alcohol can optimize the dispersion characteristics of gold particles.
Has the advantages that: compared with the prior art, the method for preparing cyclohexanone is prepared by a photocatalysis one-step method, visible light is used as a light source, air or oxygen is used as an oxidant, the reaction path is simple and direct, the reaction condition is mild and safe, the conversion rate of reaction substrate cyclohexane is high, and the selectivity of reaction product cyclohexanone is high.
Detailed Description
The invention will be further illustrated by the following specific examples, which are given for the purpose of illustration only and are not intended to be limiting.
Example 1
A method for preparing cyclohexanone uses a gold-carbon composite photocatalyst, and under the condition of visible light, a reaction substrate cyclohexane is oxidized in one step to generate cyclohexanone. The reaction conditions for oxidizing cyclohexane to form cyclohexanone are as follows: adding acetonitrile serving as a solvent, cyclohexane serving as a reaction substrate and the gold-carbon composite photocatalyst into a quartz photocatalytic reaction tube, and reacting under the condition of visible light.
Wherein, a xenon lamp of 500W is used as a light source for visible light irradiation, and an optical filter with the cut-off wavelength of 400nm is added to filter an ultraviolet band; the distance between the center of the xenon lamp and the center of the reaction tube is 150 mm.
Wherein the capacity of the photocatalytic reaction tube is 50mL, the dosage of acetonitrile serving as a solvent is 15mL, the dosage of cyclohexane is 2g, the dosage of the gold-carbon composite photocatalyst is 0.05g, and the reaction time is 6 h.
In the reaction process, the photocatalytic reaction tube is not sealed, and the actual oxidant is air.
After the reaction was completed, the conversion of cyclohexane was 36.3% and the selectivity of cyclohexanone was 98.9% as measured by an internal standard method using an Agilent 8890 gas chromatograph.
Example 2
A method for preparing cyclohexanone uses a gold-carbon composite photocatalyst, and under the condition of visible light, a reaction substrate cyclohexane is oxidized in one step to generate cyclohexanone. The reaction conditions for oxidizing cyclohexane to form cyclohexanone are as follows: adding acetonitrile serving as a solvent, cyclohexane serving as a reaction substrate and the gold-carbon composite photocatalyst into a quartz photocatalytic reaction tube, and reacting under the condition of visible light.
Wherein, a xenon lamp of 500W is used as a light source for visible light irradiation, and an optical filter with the cut-off wavelength of 400nm is added to filter an ultraviolet band; the distance between the center of the xenon lamp and the center of the reaction tube is 150 mm.
Wherein the capacity of the photocatalytic reaction tube is 50mL, the dosage of acetonitrile serving as a solvent is 15mL, the dosage of cyclohexane is 2g, the dosage of the gold-carbon composite photocatalyst is 0.05g, and the reaction time is 6 h.
In addition, a plug is also arranged at the opening of the photocatalytic reaction tube, and a condensation reflux device is arranged on the plug; a pipeline is also arranged in the plug in a penetrating way, one end of the pipeline extends into the solution, the other end of the pipeline is connected with an oxygen source, oxygen gas flows through the pipeline to bubble into the solution, and the flow rate is 5 mL/min.
In the reaction process, the photocatalytic reaction tube is provided with a plug, oxygen is used for bubbling to the reaction liquid, and the actual oxidant is oxygen.
After the reaction was completed, the conversion of cyclohexane was 43.8% and the selectivity of cyclohexanone was 97.7% as measured by an internal standard method using an Agilent 8890 gas chromatograph.
In each of the above examples, the gold-carbon composite photocatalyst used was prepared by the following steps:
preparation of S1 precursor: carrying out quaternization reaction on 4-cyano benzyl bromide and 4,4' -bipyridyl to generate a humate, thus obtaining a precursor;
briquetting of S2 precursor: filling the precursor into a tablet press and extruding into blocks;
preparation of S3 vector: carrying out heat treatment on the massive precursor prepared in the step S2 under the condition of air isolation to obtain a carrier;
s4 loading gold nanoparticles: and loading gold nanoparticles on the carrier by using a photo-deposition method to obtain the gold-carbon composite photocatalyst.
And in step S1, adding reactants 4-cyanobenzyl bromide and 4,4' -bipyridine into solvent absolute ethyl alcohol according to the molar ratio of 2:1, reacting for 8 hours at 78 ℃ with the mass ratio of the solvent to the reactants being 5:1, washing the obtained mixture for 3 times by using ethyl acetate, filtering and drying to obtain the precursor.
And, in step S2, the precursor is ground into powder, loaded into a tablet press, and pressed into a cylindrical block with a mass of 2g under a pressure of 30 MPa.
And in step S3, the massive precursor prepared in step S2 is filled into a tube furnace, high-purity nitrogen is introduced, the flow rate is 120mL/min, the temperature is raised to 520 ℃ after 20min, the temperature raising rate is 5 ℃/min, the temperature is kept for 6h, the temperature is raised to 930 ℃ again, the temperature raising rate is 2 ℃/min, the temperature is kept for 4h, then the massive precursor is naturally cooled to the room temperature, and the massive precursor is ground into powder to obtain the carrier.
And in step S4, 15mL of chloroauric acid aqueous solution with the concentration of 0.5mmol/L is filled into a photoreaction tube, 0.3g of palmityl alcohol is added, 1g of carrier is added, stirring is started, a 500W high-pressure mercury lamp is used for light reaction for 5 hours at normal temperature, and the solid is filtered, washed and dried to obtain the gold-carbon composite photocatalyst.
Wherein, the element analysis result (mass fraction) of the precursor, C: 58.0%, H: 4.5%, N: 5.6 percent; the specific surface area of the support was 2500m2(ii)/g; specific surface area of the gold-carbon composite photocatalyst is 2100m2/g。
The above embodiments are merely preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the principle of the present invention, and these modifications should also be regarded as the protection scope of the present invention.
Claims (9)
1. A process for the preparation of cyclohexanone, characterized in that: using a gold-carbon composite photocatalyst to oxidize a reaction substrate cyclohexane in one step under the condition of visible light to generate cyclohexanone;
the gold-carbon composite photocatalyst is prepared by the following steps:
preparation of S1 precursor: carrying out quaternization reaction on 4-cyano benzyl bromide and 4,4' -bipyridyl to generate a humate, thus obtaining a precursor;
briquetting of S2 precursor: filling the precursor into a tablet press and extruding into blocks;
preparation of S3 vector: carrying out heat treatment on the massive precursor prepared in the step S2 under the condition of air isolation to obtain a carrier;
s4 loading gold nanoparticles: and loading gold nanoparticles on the carrier by using a photo-deposition method to obtain the gold-carbon composite photocatalyst.
2. The process for producing cyclohexanone according to claim 1, characterized in that: the reaction conditions for oxidizing cyclohexane to form cyclohexanone are as follows: adding acetonitrile serving as a solvent, cyclohexane serving as a reaction substrate and the gold-carbon composite photocatalyst into a quartz photocatalytic reaction tube, and reacting under the condition of visible light.
3. The process for producing cyclohexanone according to claim 2, characterized in that: a light source for visible light uses a 500W xenon lamp and an optical filter with the cut-off wavelength of 400nm to filter an ultraviolet band; the distance between the center of the xenon lamp and the center of the reaction tube is 150 mm.
4. The process for producing cyclohexanone according to claim 2, characterized in that: the capacity of the photocatalytic reaction tube is 50mL, the dosage of acetonitrile serving as a solvent is 15mL, the dosage of cyclohexane is 2g, the dosage of a gold-carbon composite photocatalyst is 0.05g, and the reaction time is 6 h.
5. The process for producing cyclohexanone according to any one of claims 2 to 4, characterized in that: a plug is further arranged at the opening of the photocatalytic reaction tube, and a condensation reflux device is arranged on the plug; a pipeline is further arranged in the plug in a penetrating mode, one end of the pipeline extends into the solution, the other end of the pipeline is connected with an oxygen source, oxygen gas flows through the pipeline to bubble into the solution, and the flow rate is 5 mL/min.
6. The process for producing cyclohexanone according to claim 5, characterized in that: in step S1, reactants 4-cyanobenzyl bromide and 4,4' -bipyridyl are added into solvent absolute ethyl alcohol according to the molar ratio of 2:1, the mass ratio of the solvent to the reactants is 5:1, the mixture obtained through reaction is reacted for 8 hours at 78 ℃, the mixture obtained through reaction is washed for 3 times by ethyl acetate, and the precursor is obtained after filtration and drying.
7. The process for producing cyclohexanone according to claim 5, characterized in that: in step S2, the precursor is ground into powder, and the powder is loaded into a tablet press and pressed into a cylindrical block under a pressure of 30MPa, wherein the mass of the cylindrical block is 2 g.
8. The process for producing cyclohexanone according to claim 5, characterized in that: and step S3, filling the massive precursor prepared in the step S2 into a tube furnace, introducing high-purity nitrogen at a flow rate of 120mL/min, heating to 520 ℃ after 20min at a heating rate of 5 ℃/min, preserving heat for 6h, heating to 930 ℃ at a heating rate of 2 ℃/min, preserving heat for 4h, naturally cooling to room temperature, and grinding into powder to obtain the carrier.
9. The process for producing cyclohexanone according to claim 5, characterized in that: in step S4, 15mL of aqueous solution of chloroauric acid with concentration of 0.5mmol/L is put into a photoreaction tube, 0.3g of palmityl alcohol is added, 1g of carrier is added, stirring is started, a 500W high-pressure mercury lamp is used for light reaction for 5 hours at normal temperature, and the gold-carbon composite photocatalyst is obtained after solid is filtered out, washed and dried.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1113075A (en) * | 1965-10-23 | 1968-05-08 | Allied Chem | Process for the production of cyclohexanone |
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|---|---|---|---|---|
| GB1113075A (en) * | 1965-10-23 | 1968-05-08 | Allied Chem | Process for the production of cyclohexanone |
| CN104138757A (en) * | 2014-07-25 | 2014-11-12 | 浙江师范大学 | Titanium dioxide/metal core-shell structure composite nano-particle and preparing method thereof |
| US20160214087A1 (en) * | 2015-01-23 | 2016-07-28 | Umm Al-Qura University | GOLD LOADED TiO2 NANOTUBE-MULTIWALLED CARBON NANOTUBE COMPOSITES AS ACTIVE PHOTOCATALYSTS FOR CYCLOHEXANE OXIDATION |
| CN105664929A (en) * | 2016-01-19 | 2016-06-15 | 福州大学 | Nano-plate with precious metal and method for preparing nano-plate |
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