CN111718248B - Catalyst for preparing benzaldehyde by catalytic oxidation of styrene, preparation method thereof and method for preparing benzaldehyde - Google Patents
Catalyst for preparing benzaldehyde by catalytic oxidation of styrene, preparation method thereof and method for preparing benzaldehyde Download PDFInfo
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- CN111718248B CN111718248B CN202010752226.2A CN202010752226A CN111718248B CN 111718248 B CN111718248 B CN 111718248B CN 202010752226 A CN202010752226 A CN 202010752226A CN 111718248 B CN111718248 B CN 111718248B
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- hydrogen peroxide
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 exist Chemical compound 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
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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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing benzaldehyde by catalytic oxidation of styrene, a preparation method thereof and a method for preparing benzaldehyde, and belongs to the technical field of preparation of organic chemicals. The catalyst is formed by nano particles with the particle size of less than 100nm coated by graphene oxide, the dispersibility of the graphene oxide in a reaction system can be effectively improved by the nano particles, the oxidation capability of hydrogen peroxide can be improved by the graphene oxide, and the selectivity of a target product benzaldehyde can be improved by the nano particles. The catalyst has high catalytic selectivity, and the purity of the product and the atomic utilization rate of the reaction can be improved by reasonably controlling the mass molar ratio of the catalyst to the styrene and the hydrogen peroxide in the reaction system, so that the difficulty of subsequent separation and purification is reduced. The catalyst has simple preparation method, does not need to add solvents or other auxiliary agents during the preparation process, and has good industrial application prospect. The method for preparing the benzaldehyde is simple to operate, environment-friendly, less in byproduct of the prepared benzaldehyde, easy to separate and purify, and suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of preparation of organic chemicals, and particularly relates to a catalyst for preparing benzaldehyde by catalytic oxidation of styrene, a preparation method of the catalyst and a method for preparing benzaldehyde.
Background
At present, two industrial production methods of benzaldehyde mainly exist, one is to hydrolyze benzyl dichloride to prepare benzaldehyde, and the other is to oxidize toluene to prepare benzaldehyde. Wherein, the benzaldehyde prepared by the benzyl dichloride hydrolysis method contains chlorine element to influence the purity and application of the product. In the whole process of the toluene oxidation method, chlorine is not contained, but in the reaction, the product benzaldehyde is easy to continue to be oxidized into benzoic acid due to the large temperature or pressure of the reaction, so that the yield of the benzaldehyde is reduced, and the recovery and treatment cost of the byproduct benzoic acid is increased.
The double bond of styrene has very high reactivity. Under a certain temperature, the carbon-carbon double bond is easy to break under the action of a catalyst, so that reactions such as addition, oxidation and the like occur. And the catalyst is subjected to selective oxidation reaction with an oxidant to generate products such as phenyl ethylene oxide, phenylacetaldehyde, benzaldehyde, benzoic acid, acetophenone, phenethyl alcohol and the like.
The product after the oxidation reaction of the oxidant hydrogen peroxide is water, the environment is protected, the post treatment is easier, the development concept of green chemical industry is met, but the oxidation capability and the selectivity of the hydrogen peroxide to the product are weaker, the catalytic activity is high, and the catalyst with good selectivity are cooperated to improve the yield and the selectivity of the reaction product. Therefore, a catalyst with high catalytic activity and good selectivity needs to be developed to catalyze the oxidation reaction of styrene to prepare benzaldehyde.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a catalyst for preparing benzaldehyde by catalytic oxidation of styrene; second, a process for preparing the catalyst is provided; and a third purpose is to provide a method for preparing benzaldehyde by catalytic oxidation of styrene by the catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a catalyst for preparing benzaldehyde by catalytic oxidation of styrene, which is formed by graphene oxide coated nano particles with particle size below 100 nm.
Preferably, the mass ratio of graphene oxide to nano particles in the catalyst is 3:7-17.
Preferably, the nanoparticle is nano ZSM-5.
2. The preparation method of the catalyst for preparing benzaldehyde by catalytic oxidation of styrene comprises the following steps:
adding nano particles with the particle size below 100nm into the graphene oxide solution under stirring, and vacuumizing until no liquid exists.
3. The method for preparing benzaldehyde by using the catalyst to catalyze and oxidize styrene comprises the following steps:
sequentially adding styrene, hydrogen peroxide solution and the catalyst into an organic solvent, stirring at 45-75 ℃ for reaction for 6-12 hours, centrifuging to obtain supernatant, transferring the supernatant into a separating funnel for separating to obtain an organic phase and a water phase respectively, washing the organic phase to be neutral, neutralizing the water phase to be pH value of 8-9, extracting to obtain an extract, merging the organic phase washed to be neutral and the extract, and performing vacuum rotary evaporation to obtain benzaldehyde.
Preferably, the mass molar ratio of the catalyst to the styrene and the hydrogen peroxide in the organic solvent is 0.5-5:1:1-4, and g: mol.
Preferably, the organic solvent is one of methanol, acetonitrile or dioxane.
Preferably, the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 27-50%.
Preferably, ethyl acetate is added for the separation.
Preferably, the method of washing the organic phase to neutrality is as follows: washing with 5% sodium bicarbonate aqueous solution for 3-5 times, and washing with distilled water to neutrality.
Preferably, the method of neutralizing the aqueous phase to a pH of 8-9 is as follows: the aqueous phase was neutralized to a pH of 8-9 with 5% by mass aqueous sodium bicarbonate solution.
Preferably, ethyl acetate is added for extraction.
The invention has the beneficial effects that: the invention provides a catalyst for preparing benzaldehyde by catalyzing and oxidizing styrene, a preparation method thereof and a preparation method of benzaldehyde, wherein the catalyst is formed by coating nano particles with particle diameters below 100nm by graphene oxide, wherein the nano particles with particle diameters below 100nm can effectively improve the dispersibility of the graphene oxide in a reaction system, ensure that the graphene oxide is uniformly dispersed in the reaction system and does not settle, so that the graphene oxide can fully contact with styrene and hydrogen peroxide in the reaction system, and plays a bridge role in the process, so that styrene and hydrogen peroxide with larger polarity difference are aggregated on the surface of the graphene oxide, thereby improving the oxidation capacity and the utilization efficiency of the hydrogen peroxide, and further improving the dispersibility of the graphene oxide in the reaction system by controlling the content of the graphene oxide in a composite material. The epoxy bond and carboxyl in the graphene oxide in the catalyst can be combined with hydrogen peroxide to form a peroxy bond, and the oxidation capacity of the generated peroxy bond is larger than that of the hydrogen peroxide, so that the oxidation capacity of the hydrogen peroxide can be improved, and ineffective decomposition of the hydrogen peroxide can be avoided; the nano particles in the catalyst improve the selectivity of the target product benzaldehyde, wherein the nano ZSM-5 is beneficial to the generation of the oxidation product benzaldehyde due to the specific pore channel structure of the nano ZSM-5, is not beneficial to the generation of products such as phenyl ethylene oxide, phenylacetaldehyde, benzoic acid, acetophenone, phenethyl alcohol and the like, and is also not beneficial to the further catalytic oxidation of the oxidation product benzaldehyde into benzoic acid. The catalyst has high catalytic selectivity, and the purity of the product and the atomic utilization rate of the reaction can be improved by reasonably controlling the mass molar ratio of the catalyst to the styrene and the hydrogen peroxide in the reaction system, so that the difficulty of subsequent separation and purification is reduced. The catalyst has simple preparation method, does not need to add solvents or other auxiliary agents during the preparation process, and has good industrial application prospect. The method for preparing the benzaldehyde is simple to operate, is environment-friendly, has few byproducts, is easy to separate and purify, and is suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
(1) Adding nano ZSM-5 with the particle size below 100nm into graphene oxide solution under stirring according to the mass ratio of the graphene oxide to the nano ZSM-5 of 3:7, and vacuumizing until no liquid exists, so as to obtain a catalyst;
(2) Sequentially adding styrene, a 40% hydrogen peroxide solution and the catalyst prepared in the step (1) into dioxane, wherein the mass molar ratio of the added catalyst to the styrene and the hydrogen peroxide is 3:1:3, g: mol, stirring and reacting for 12 hours at 45 ℃, centrifuging to obtain a supernatant, transferring the supernatant to a separating funnel, adding ethyl acetate to separate liquid to obtain an organic phase and a water phase, washing the organic phase with a 5% sodium bicarbonate aqueous solution for 3 times, washing the organic phase with distilled water to be neutral, neutralizing the water phase with a 5% sodium bicarbonate aqueous solution for pH value of 8, adding ethyl acetate for extraction to obtain an extract, combining the washed neutral organic phase with the extract, and performing vacuum rotary evaporation to obtain benzaldehyde, wherein the conversion rate of the styrene is 100% and the selectivity of the benzaldehyde is 98% as known by weighing and liquid chromatography analysis.
Example 2
(1) Adding nano ZSM-5 with the particle size below 100nm into graphene oxide solution under stirring according to the mass ratio of the graphene oxide to the nano ZSM-5 of 3:17, and vacuumizing until no liquid exists to prepare the catalyst;
(2) Sequentially adding styrene, a hydrogen peroxide solution with the mass fraction of 50% and the catalyst prepared in the step (1), wherein the mass molar ratio of the added catalyst to the styrene and the hydrogen peroxide is 0.5:1:1, g: mol, stirring and reacting for 8 hours at 60 ℃, centrifuging to obtain a supernatant, transferring the supernatant to a separating funnel, adding ethyl acetate to separate liquid to obtain an organic phase and a water phase, washing the organic phase with a sodium bicarbonate aqueous solution with the mass fraction of 5% for 5 times, washing the organic phase with distilled water to be neutral, neutralizing the water phase with a sodium bicarbonate aqueous solution with the mass fraction of 5% to the pH value of 8, adding ethyl acetate for extraction to obtain an extract, combining the washed organic phase with the extract to be neutral, and performing vacuum rotary evaporation to obtain benzaldehyde, wherein the conversion rate of the styrene is 70% and the selectivity of the benzaldehyde is 98% as known by weighing and liquid chromatography analysis.
Example 3
(1) Adding nano ZSM-5 with the particle size below 100nm into graphene oxide solution under stirring according to the mass ratio of the graphene oxide to the nano ZSM-5 of 3:12, and vacuumizing until no liquid exists, so as to obtain a catalyst;
(2) Sequentially adding styrene, a hydrogen peroxide solution with the mass fraction of 27% and the catalyst prepared in the step (1), wherein the mass molar ratio of the added catalyst to the styrene and the hydrogen peroxide is 5:1:4, g: mol, stirring and reacting for 6 hours at 75 ℃, centrifuging to obtain a supernatant, transferring the supernatant to a separating funnel, adding ethyl acetate for separating liquid to obtain an organic phase and a water phase respectively, washing the organic phase with a sodium bicarbonate aqueous solution with the mass fraction of 5% for 4 times, washing the organic phase with distilled water to be neutral, neutralizing the water phase with a sodium bicarbonate aqueous solution with the mass fraction of 5% to the pH value of 9, adding ethyl acetate for extraction to obtain an extract, combining the washed neutral organic phase with the extract, and performing vacuum rotary evaporation to obtain benzaldehyde, wherein the conversion rate of the styrene is 95% and the selectivity of the benzaldehyde is 90% as known by weighing and liquid chromatography analysis.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (6)
1. A method for preparing benzaldehyde by catalytic oxidation of styrene by using a catalyst, which is characterized by comprising the following steps: sequentially adding styrene, a hydrogen peroxide solution and a catalyst into an organic solvent, stirring at 45-75 ℃ for reaction for 6-12 hours, centrifuging to obtain a supernatant, transferring the supernatant into a separating funnel for separating liquid to obtain an organic phase and a water phase respectively, washing the organic phase to be neutral, neutralizing the water phase to be pH 8-9, extracting to obtain an extract, merging the organic phase washed to be neutral and the extract, and performing vacuum rotary evaporation to obtain benzaldehyde;
the catalyst is formed by nano particles with particle diameters of less than 100nm coated by graphene oxide; the mass ratio of graphene oxide to nano particles in the catalyst is 3:7-17; the nano particles are nano ZSM-5;
the preparation method of the catalyst comprises the steps of adding nano particles with the particle size of less than 100nm into graphene oxide solution under stirring, and vacuumizing until no liquid exists.
2. The method according to claim 1, wherein the mass molar ratio of catalyst to styrene and hydrogen peroxide in the organic solvent is 0.5-5:1:1-4, g: mol.
3. The method of claim 1, wherein the organic solvent is one of methanol, acetonitrile, or dioxane.
4. The method of claim 1, wherein the hydrogen peroxide solution comprises 27-50% hydrogen peroxide by mass.
5. The process according to claim 1, characterized in that the organic phase is washed to neutrality as follows: washing with 5% sodium bicarbonate aqueous solution for 3-5 times, and washing with distilled water to neutrality.
6. The process according to claim 1, characterized in that the aqueous phase is neutralized to a pH value of 8-9 as follows: the aqueous phase was neutralized to a pH of 8-9 with 5% by mass aqueous sodium bicarbonate solution.
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