CN108250056B - Catalytic synthesis method of benzaldehyde - Google Patents
Catalytic synthesis method of benzaldehyde Download PDFInfo
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- CN108250056B CN108250056B CN201810232998.6A CN201810232998A CN108250056B CN 108250056 B CN108250056 B CN 108250056B CN 201810232998 A CN201810232998 A CN 201810232998A CN 108250056 B CN108250056 B CN 108250056B
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalytic synthesis method of benzaldehyde. The invention firstly uses ZrO2And NH4VO3Adding into sulfuric acid solution, stirring and refluxing, washing solid product, drying and roasting to obtain SO4 2‑/V2O5‑ZrO2Compounding catalyst, and using SO under the condition of using hydrogen peroxide as oxidant4 2‑/V2O5‑ZrO2The composite catalyst catalyzes styrene to synthesize benzaldehyde. The method has the advantages of high efficiency of catalytic synthesis of benzaldehyde, environmental friendliness, mild reaction conditions, easily available raw materials and low production cost, the conversion rate of styrene reaches 61.3%, and the selectivity of benzaldehyde can reach 100% at most. SO (SO)4 2‑/V2O5‑ZrO2The composite catalyst has the advantages of large specific surface area, high catalytic activity, adjustable surface acidity, high hydrothermal stability, simple preparation process, high selectivity, less side reaction, no corrosion to equipment, no three-waste pollution and renewable and reusable property.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalytic synthesis method of benzaldehyde.
Background
Benzaldehyde is an important chemical raw material and an important organic reaction intermediate, and is widely used in the fields of spices, dyes, medicines, pesticides, foods and the like. At present, the domestic industrial production of benzaldehyde mostly adopts a benzyl chloride hydrolysis method, and the generated benzaldehyde contains chloride, so that the production equipment is easily corroded and the environment is easily polluted, and the production of benzaldehyde by the method is limited. Although some progress has been made in the method of synthesizing benzaldehyde by oxidizing toluene, the method still has the disadvantages of low reaction conversion rate and selectivity, long reaction time, easy environmental pollution caused by applying organic solvent, etc. With the improvement of the social requirement on environmental protection in recent years, how to provide a more efficient and environment-friendly catalyst and a novel benzaldehyde catalytic synthesis method become problems to be solved in the technical field of organic synthesis.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a catalytic synthesis method of benzaldehyde.
The technical scheme of the invention is as follows:
the catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
ZrO is mixed according to a certain mass ratio2And NH4VO3Adding the mixture into a sulfuric acid solution with a certain mass concentration, stirring and refluxing at a certain temperature, performing vacuum filtration to obtain a solid product, washing the solid product to be neutral, drying, and roasting at a certain temperature to obtain SO4 2-/V2O5-ZrO2A composite catalyst;
step two, catalytic synthesis of benzaldehyde:
preparing the SO prepared in the step one according to a certain mass-to-volume ratio4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, and mixing SO4 2-/V2O5-ZrO2Adding the composite catalyst into styrene, stirring and refluxing under the condition of temperature rise, adding hydrogen peroxide into a reaction system when the temperature rises to a certain temperature, keeping the temperature, continuously stirring and refluxing for a certain time, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Further, step one said ZrO2And NH4VO3The mass ratio of the sulfuric acid solution to the sulfuric acid is 1: 0.1-2, the mass concentration of the sulfuric acid solution is 5-50%, the stirring reflux temperature is 20-30 ℃, and the stirring reflux time is 10-20 hours.
Further, step one said ZrO2And NH4VO3The mass ratio of (1: 0.6) - (1.4 g), and the mass concentration of the sulfuric acid solution is 9-33%.
Further, in the step one, the drying condition is drying for 5-10 hours at 100-150 ℃.
Further, in the step one, roasting is carried out for 1-5 hours in a muffle furnace at 400-900 ℃.
Further, in the first step, the roasting condition is 400-600 ℃.
Further, SO in step two4 2-/V2O5-ZrO2The mass volume ratio of the composite catalyst to the styrene to the hydrogen peroxide is (0.1-0.5) g: (1-5) mL: (1-10) mL.
Further, in the second step, the temperature of the reaction system is 50-100 ℃ when hydrogen peroxide is added, and the mass concentration of the hydrogen peroxide is 30%.
And further, after adding hydrogen peroxide into the reaction system in the step two, continuously stirring and refluxing for 3-9 hours.
The invention has the beneficial effects that:
the invention utilizes SO4 2-/V2O5-ZrO2The composite catalyst has the advantages of high efficiency of catalytic synthesis of benzaldehyde, environmental friendliness, mild reaction conditions, easily available raw materials and low production cost, the conversion rate of styrene reaches 61.3%, and the selectivity of benzaldehyde can reach 100% at most. SO of the invention4 2-/V2O5-ZrO2The composite catalyst has the advantages of large specific surface area, high catalytic activity, surface acidity adjustability, high hydrothermal stability, simple preparation process, high selectivity, less side reaction, no corrosion to equipment, no three-waste pollution, reproducibility and reusability, and the like.
Drawings
FIG. 1 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 13;
FIG. 2 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 15;
FIG. 3 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 16.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
ZrO is mixed according to a certain mass ratio2And NH4VO3Adding the mixture into a sulfuric acid solution with a certain mass concentration, stirring and refluxing at a certain temperature, performing vacuum filtration to obtain a solid product, washing the solid product to be neutral, drying, and roasting at a certain temperature to obtain SO4 2-/V2O5-ZrO2A composite catalyst;
step two, catalytic synthesis of benzaldehyde:
preparing the SO prepared in the step one according to a certain mass-to-volume ratio4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, and mixing SO4 2-/V2O5-ZrO2Adding the composite catalyst into styrene, stirring and refluxing under the condition of temperature rise, adding hydrogen peroxide into a reaction system when the temperature rises to a certain temperature, keeping the temperature, continuously stirring and refluxing for a certain time, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 2
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
ZrO is mixed according to the mass ratio of 1: 0.1-22And NH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 5-50%, uniformly mixing, stirring and refluxing for 10-20 hours at the temperature of 20-30 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying for 5-10 hours in a drying box at the temperature of 100-150 ℃, and roasting for 1-5 hours in a muffle furnace at the temperature of 400-900 ℃ to obtain SO4 2-/V2O5-ZrO2A composite catalyst;
step two, catalytic synthesis of benzaldehyde:
SO prepared according to step one4 2-/V2O5-ZrO2The mass volume ratio of the composite catalyst to the styrene to the hydrogen peroxide is (0.1-0.5) g: (1-5) mL: (1-10) mL of prepared SO4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, wherein the mass concentration of the hydrogen peroxide is 30 percent, and SO is added4 2-/V2O5-ZrO2Adding the composite catalyst into styrene, stirring and refluxing under the condition of temperature rise, adding hydrogen peroxide into a reaction system when the temperature rises to 50-100 ℃, keeping the temperature, continuously stirring and refluxing for 3-9 hours, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
The device for completing the catalytic reaction in the embodiment consists of a heat collection type constant temperature magnetic stirrer, a constant temperature water bath kettle and a three-neck flask with mechanical stirring and good sealing performance.
Example 3
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding into 23% sulfuric acid solution, mixing, stirring and refluxing at 25 deg.C for 12 hr,cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6 hours, and roasting the dried product in a muffle furnace at 400 ℃ for 2 hours to obtain SO4 2-/V2O5-ZrO2Composite catalyst-3;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 4
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 450 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-4;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and adding the solid catalyst into the mixture to be subjected to reactionRectifying the filtrate to obtain benzaldehyde.
Example 5
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-5;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 6
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 550 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-6;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 7
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 600 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-7;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 8
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 0.6gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-8;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 9
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 0.8gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-9;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise to 80 DEG CAdding 8.0mL of 30% hydrogen peroxide solution into the reaction system, continuously stirring and refluxing for 3h at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 10
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-10;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 11
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.2gNH4VO3Adding into 23% sulfuric acid solution, mixing, stirring and refluxing at 25 deg.C for 12 hr, cooling to room temperature, vacuum filtering to obtain solid product, and mixing with the above solidWashing the product with distilled water to neutrality, drying in a drying oven at 120 deg.C for 6 hr, and calcining in a muffle furnace at 500 deg.C for 2 hr to obtain SO4 2-/V2O5-ZrO2Composite catalyst-11;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 12
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.4gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-12;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 13
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a 9 mass percent sulfuric acid solution, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-13;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 14
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 17%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-14;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 15
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 28%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-15;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Example 16
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
1.0g of ZrO2And 1.0gNH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 33%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/V2O5-ZrO2Composite catalyst-16;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/V2O5-ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Comparative example 1
The catalytic synthesis method of benzaldehyde comprises the following steps:
step one, preparing SO4 2-/ZrO2Composite catalyst:
1.0g of ZrO2Adding the mixture into a sulfuric acid solution with the mass concentration of 23%, uniformly mixing, stirring and refluxing for 12h at 25 ℃, cooling to room temperature, carrying out vacuum filtration to obtain a solid product, washing the solid product to be neutral by using distilled water, drying the solid product in a drying box at 120 ℃ for 6h, and roasting the dried product in a muffle furnace at 500 ℃ for 2h to obtain SO4 2-/ZrO2A composite catalyst;
step two, catalytic synthesis of benzaldehyde:
0.2g of SO obtained in step one4 2-/ZrO2Adding the composite catalyst into 3.0mL of styrene, stirring and refluxing under the condition of temperature rise, adding 8.0mL of 30% hydrogen peroxide into the reaction system when the temperature is raised to 80 ℃, continuously stirring and refluxing for 3 hours at 80 ℃, naturally cooling the reaction system to room temperature, adding toluene into the extraction reaction systemFiltering the benzaldehyde to remove the solid catalyst, and rectifying the filtrate to obtain the benzaldehyde.
Analysis of catalytic Effect of the catalytic Synthesis methods of benzaldehyde of examples 3 to 16 and comparative example 1:
after the catalytic synthesis of benzaldehyde in the second step of examples 3 to 16 and comparative example 1 was completed and the extraction of benzaldehyde with toluene was completed, samples of organic phases were collected, respectively, and the samples were subjected to gas chromatography analysis to calculate the conversion of styrene and the selectivity of benzaldehyde, respectively, using the following formulas:
the conversion of benzaldehyde is calculated by the formula Con ═ n1+n2)/n0×100％；
The selectivity of benzaldehyde is calculated by the formula of Sel ═ n1/(n1+n2)×100％；
In the formula, n0-Amount of styrene charged, n1-Amount of benzaldehyde-generating substance, n2-The amount of benzoic acid producing material;
the results are shown in table 1:
TABLE 1
| Test item | Conversion of styrene (%) | Selectivity to benzaldehyde (%) |
| Example 3 | 44.32 | 95.73 |
| Example 4 | 47.04 | 94.21 |
| Example 5 | 50.8 | 90.84 |
| Example 6 | 53.5 | 87.1 |
| Example 7 | 45.72 | 92.7 |
| Example 8 | 61.3 | 79.5 |
| Example 9 | 60.8 | 80.4 |
| Example 10 | 50.6 | 93.8 |
| Example 11 | 40.5 | 95.6 |
| Example 12 | 43.9 | 95.7 |
| Example 13 | 44.3 | 100 |
| Example 14 | 42.1 | 94.6 |
| Example 15 | 58.9 | 80.23 |
| Example 16 | 48.8 | 91.8 |
| Comparative example 1 | 36.2 | 66.26 |
As can be seen from the styrene conversion and benzaldehyde selectivity data for examples 3-16 in Table 1, different ZrO temperatures were used with different catalyst calcination temperatures2And NH4VO3And SO prepared at different sulfuric acid concentrations4 2-/V2O5-ZrO2The conversion rate of the composite catalyst for catalyzing styrene is over 40 percent, and the highest conversion rate can reach 61.3 percent; the selectivity of benzaldehyde is above 70%, wherein the selectivity of 10 examples is above 90%, and the highest selectivity of benzaldehyde is 100%. And SO prepared in comparative example 14 2-/-ZrO2The conversion rate of the composite catalyst for catalyzing styrene is only 36.2%, the selectivity of benzaldehyde is only 66.26%, and therefore, V in the composite catalyst can be seen2O5Introduction of (2) stabilizes ZrO2Crystal phase of increased SO4 2-The decomposition temperature of (a) enhances the stability of the catalyst, thereby enabling SO4 2-/V2O5-ZrO2The composite catalyst has a content of SO higher than that of the catalyst4 2-/-ZrO2Catalytic activity of the composite catalyst.
Preparation of SO4 2-/V2O5-ZrO2The optimum condition of the composite catalyst is that the calcination temperature is 500 ℃, ZrO2And NH4VO 3The mass ratio of (1) to (1) and the sulfuric acid concentration of 23%.
FIG. 1 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 13; in the figure, the peak at 2.993min is the peak of toluene, the peak area is 1254997.1, the peak at 3.787min is the peak of styrene, the peak area is 95203.3, the peak at 4.471min is the peak of benzaldehyde product, and the peak area is 39542.6.
FIG. 2 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 15; in the figure, the peak at 3.061min is the peak of toluene, peak area 2292175.3, the peak at 3.914min is the peak of styrene, peak area 42015.9, the peak at 4.503min is the peak of benzaldehyde product, and peak area 39520.4.
FIG. 3 is a gas chromatogram of the toluene-extracted organic phase after the completion of the catalytic benzaldehyde synthesis reaction in example 16; in the figure, the peak appearing at 3.02min is the peak of toluene, the peak area is 1639356.5, the peak appearing at 3.857min is the peak of styrene, the peak area is 241495.5, the peak appearing at 4.477min is the peak of the product benzaldehyde, and the peak area is 34905.5.
Claims (4)
1. A catalytic synthesis method of benzaldehyde is characterized by comprising the following steps:
step one, preparing SO4 2-/V2O5-ZrO2Composite catalyst:
ZrO is mixed according to the mass ratio of 1: 0.1-22And NH4VO3Adding the mixture into a sulfuric acid solution with the mass concentration of 5-50%, stirring and refluxing at the temperature of 20-30 ℃ for 10-20 h, performing vacuum filtration to obtain a solid product, washing the solid product to be neutral, drying, and roasting in a muffle furnace at the temperature of 400-900 ℃ for 1-5 h to obtain SO4 2-/V2O5-ZrO2A composite catalyst;
step two, catalytic synthesis of benzaldehyde:
according to the mass volume ratio (0.1-0.5) g: (1-5) mL: (1-10) mL of SO prepared in the first step4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, and mixing SO4 2-/V2O5-ZrO2Adding the composite catalyst into styrene, stirring and refluxing under the condition of temperature rise, adding hydrogen peroxide with the mass concentration of 30% into a reaction system when the temperature rises to 50-100 ℃, keeping the temperature, continuously stirring and refluxing for 3-9 hours, naturally cooling the reaction system to room temperature, adding toluene to extract benzaldehyde in the reaction system, filtering to remove the solid catalyst, and rectifying filtrate to obtain the benzaldehyde.
2. The catalytic synthesis method of benzaldehyde according to claim 1, characterized in that step one of ZrO 22And NH4VO3The mass ratio of (1: 0.6) - (1.4 g), and the mass concentration of the sulfuric acid solution is 9-33%.
3. The catalytic synthesis method of benzaldehyde according to claim 2, wherein the drying condition in step one is drying at 100-150 ℃ for 5-10 h.
4. The catalytic synthesis method of benzaldehyde according to claim 3, wherein the calcination condition in step one is 400-600 ℃.
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| CN106565633A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Styrene oxidation method |
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| Highly selective oxidation of methanol to dimethoxymethane over SO42-/V2O5-ZrO2;Meng Tao等;《New J.Chem.》;20171231;第8370-8376页 * |
| Oxidation of styrene to benzaldehyde by p-toluenesulfonic acid using hydrogen peroxide in the presence of activated carbon;Nianzhe Li等;《Chinese Journal of Catalysis》;20151231;第721-727页 * |
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