CN108250056A - A kind of process for catalytic synthesis of benzaldehyde - Google Patents
A kind of process for catalytic synthesis of benzaldehyde Download PDFInfo
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- CN108250056A CN108250056A CN201810232998.6A CN201810232998A CN108250056A CN 108250056 A CN108250056 A CN 108250056A CN 201810232998 A CN201810232998 A CN 201810232998A CN 108250056 A CN108250056 A CN 108250056A
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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
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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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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Abstract
The invention belongs to technical field of organic synthesis more particularly to a kind of process for catalytic synthesis of benzaldehyde.The present invention is first by ZrO2And NH4VO3It is added in sulfuric acid solution by being stirred at reflux, solid product washs, dry and roasting obtains SO4 2‑/V2O5‑ZrO2Composite catalyst, then SO is utilized under conditions of hydrogen peroxide is as oxidant4 2‑/V2O5‑ZrO2The styrene catalyzed synthesizing benzaldehyde of composite catalyst.The present invention catalyzes and synthesizes that benzaldehyde is efficient, environmental-friendly, reaction condition is mild, raw material is easy to get, and production cost is low, and the conversion ratio of styrene reaches 61.3%, and the selectivity of benzaldehyde reaches as high as 100%.SO4 2‑/V2O5‑ZrO2Composite catalyst large specific surface area, catalytic activity are high, surface acidity can modulation, hydrothermal stability is high, preparation process is simple, high selectivity, side reaction are few, not etching apparatus, without " three wastes " pollution, renewable reuse.
Description
Technical field
The invention belongs to technical field of organic synthesis more particularly to a kind of process for catalytic synthesis of benzaldehyde.
Background technology
Benzaldehyde is a kind of important industrial chemicals, while is also a kind of important organic reaction intermediate, is widely used in
The fields such as fragrance, dyestuff, medicine, pesticide, food.At present, domestic industry production benzaldehyde is largely using benzyl chloride hydrolysis
Method contains chloride in the benzaldehyde of generation, easily causes corrosion and environmental pollution to production equipment, therefore cause with the party
Method production benzaldehyde is restricted.Although directly being had made some progress by the method for toluene oxidation synthesizing benzaldehyde, but still deposit
Reaction conversion ratio and selectivity it is low, the reaction time is long, easily cause environmental pollution using organic solvent the shortcomings of.In recent years with
Raising of the society to environmental requirement, how a kind of more efficient, environmental-friendly catalyst is provided and the catalysis of new benzaldehyde is closed
Become technical field of organic synthesis urgent problem to be solved into method.
Invention content
To solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of process for catalytic synthesis of benzaldehyde.
Technical scheme of the present invention：
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By certain mass than ZrO2And NH4VO3It is added in the sulfuric acid solution of certain mass concentration, at a certain temperature
Completion is stirred at reflux, and decompression filters and obtains solid product, and the solid product is washed to neutrality and after drying, is placed in a constant temperature
It is roasted under degree, obtains SO4 2-/V2O5-ZrO2Composite catalyst；
Step 2: catalyze and synthesize benzaldehyde：
The SO as made from certain mass volume ratio gets step 1 ready4 2-/V2O5-ZrO2Composite catalyst, styrene and dioxygen
Water, by SO4 2-/V2O5-ZrO2Composite catalyst is added in styrene, is stirred at reflux under Elevated Temperature Conditions, is risen to certain temperature
When added in into reaction system and hydrogen peroxide and the temperature kept to continue to be stirred at reflux after a certain period of time, make reaction system naturally cold
But to room temperature, the benzaldehyde in toluene extraction reaction system is added in, solid catalyst is filtered to remove, filtrate rectifying is obtained into benzene first
Aldehyde.
Further, ZrO described in step 12And NH4VO3Mass ratio be 1:0.1~2, the quality of the sulfuric acid solution is dense
It is 5~50% to spend, and the temperature that is stirred at reflux is 20~30 DEG C, is stirred at reflux the time as 10~20h.
Further, ZrO described in step 12And NH4VO3Mass ratio be 1:0.6~1.4g, the matter of the sulfuric acid solution
Measure a concentration of 9~33%.
Further, drying condition described in step 1 is 100~150 DEG C of dry 5~10h.
Further, roasting condition described in step 1 roasts 1~5h for 400~900 DEG C of Muffle furnaces.
Further, roasting condition described in step 1 is 400~600 DEG C.
Further, SO described in step 24 2-/V2O5-ZrO2The mass volume ratio of composite catalyst, styrene and hydrogen peroxide
For (0.1~0.5) g：(1~5) mL：(1~10) mL.
Further, the temperature of reaction system is 50~100 DEG C when hydrogen peroxide is added in described in step 2, the dioxygen water quality
Measure a concentration of 30%.
Further, reaction system described in step 2 continues the time being stirred at reflux as 3~9h after adding in hydrogen peroxide.
Beneficial effects of the present invention：
The present invention utilizes SO4 2-/V2O5-ZrO2Composite catalyst catalyze and synthesize benzaldehyde it is efficient, it is environmental-friendly, reaction item
Part is mild, raw material is easy to get, and production cost is low, and the conversion ratio of styrene reaches 61.3%, and the selectivity of benzaldehyde reaches as high as
100%.SO of the present invention4 2-/V2O5-ZrO2Composite catalyst have large specific surface area, catalytic activity be high, surface acidity can modulation,
Hydrothermal stability is high, preparation process is simple, high selectivity, side reaction is few, etching apparatus, nothing " three wastes " do not pollute, are renewable heavy
The advantages that using again.
Description of the drawings
Fig. 1 be embodiment 13 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram；
Fig. 2 be embodiment 15 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram；
Fig. 3 be embodiment 16 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram.
Specific embodiment
With reference to embodiment, the following further describes the technical solution of the present invention, and however, it is not limited to this, every right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention, should all be contained
It covers in protection scope of the present invention.
Embodiment 1
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By certain mass than ZrO2And NH4VO3It is added in the sulfuric acid solution of certain mass concentration, at a certain temperature
Completion is stirred at reflux, and decompression filters and obtains solid product, and the solid product is washed to neutrality and after drying, is placed in a constant temperature
It is roasted under degree, obtains SO4 2-/V2O5-ZrO2Composite catalyst；
Step 2: catalyze and synthesize benzaldehyde：
The SO as made from certain mass volume ratio gets step 1 ready4 2-/V2O5-ZrO2Composite catalyst, styrene and dioxygen
Water, by SO4 2-/V2O5-ZrO2Composite catalyst is added in styrene, is stirred at reflux under Elevated Temperature Conditions, is risen to certain temperature
When added in into reaction system and hydrogen peroxide and the temperature kept to continue to be stirred at reflux after a certain period of time, make reaction system naturally cold
But to room temperature, the benzaldehyde in toluene extraction reaction system is added in, solid catalyst is filtered to remove, filtrate rectifying is obtained into benzene first
Aldehyde.
Embodiment 2
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
It is 1 by mass ratio:0.1~2 ZrO2And NH4VO3It is added in the sulfuric acid solution that mass concentration is 5~50%, mixes
After closing uniformly, 10~20h is stirred at reflux at 20~30 DEG C, is cooled to room temperature, decompression filters and obtains solid product, will be described solid
Body product is washed with distilled water to neutrality and in 100~150 DEG C of drying box after dry 5~10h, is placed in 400~900 DEG C of horses
Not 1~5h of kiln roasting obtains SO4 2-/V2O5-ZrO2Composite catalyst；
Step 2: catalyze and synthesize benzaldehyde：
The SO as made from step 14 2-/V2O5-ZrO2The mass volume ratio of composite catalyst, styrene and hydrogen peroxide is
(0.1~0.5) g：(1~5) mL：(1~10) mL gets SO ready4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, it is described
Hydrogen peroxide mass concentration is 30%, by SO4 2-/V2O5-ZrO2Composite catalyst is added in styrene, is stirred under Elevated Temperature Conditions
Reflux adds in hydrogen peroxide into reaction system when rising to 50~100 DEG C and the temperature is kept to continue to be stirred at reflux 3~9h, makes
Reaction system cooled to room temperature adds in the benzaldehyde in toluene extraction reaction system, is filtered to remove solid catalyst, will filter
Liquid rectifying obtains benzaldehyde.
The present embodiment by heat collecting type constant temperature blender with magnetic force, thermostat water bath and carries for completing the device of catalysis reaction
The three-neck flask composition of churned mechanically good airproof performance.
Embodiment 3
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 400 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -3；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 4
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 450 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -4；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 5
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -5；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 6
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 550 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -6；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 7
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 600 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -7；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 8
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 0.6gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -8；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 9
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 0.8gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -9；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 10
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -10；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 11
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.2gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -11；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 12
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.4gNH4VO3It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -12；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 13
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 9%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -13；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 14
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 17%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -14；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 15
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 28%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -15；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Embodiment 16
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By 1.0gZrO2And 1.0gNH4VO3It is added in the sulfuric acid solution that mass concentration is 33%, after mixing, 25
12h is stirred at reflux at DEG C, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to
Neutrality simultaneously after dry 6h, is placed in 500 DEG C of Muffle kiln roasting 2h, obtains SO in 120 DEG C of drying box4 2-/V2O5-ZrO2It is compound
Catalyst -16；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/V2O5-ZrO2Composite catalyst is added in 3.0mL styrene, in heating item
It is stirred at reflux under part, adds in hydrogen peroxide simultaneously 80 DEG C of continuation that 8.0mL mass concentrations are 30% when rising to 80 DEG C into reaction system
3h is stirred at reflux, makes reaction system cooled to room temperature, the benzaldehyde in toluene extraction reaction system is added in, is filtered to remove solid
Filtrate rectifying is obtained benzaldehyde by body catalyst.
Comparative example 1
A kind of process for catalytic synthesis step of benzaldehyde is as follows：
Step 1: prepare SO4 2-/ZrO2Composite catalyst：
By 1.0gZrO2It is added in the sulfuric acid solution that mass concentration is 23%, after mixing, is stirred back at 25 DEG C
12h is flowed, is cooled to room temperature, decompression filters and obtains solid product, and the solid product is washed with distilled water to neutrality and in 120
DEG C drying box in after dry 6h, be placed in 500 DEG C of Muffle kiln roasting 2h, obtain SO4 2-/ZrO2Composite catalyst；
Step 2: catalyze and synthesize benzaldehyde：
By SO made from 0.2g step 14 2-/ZrO2Composite catalyst is added in 3.0mL styrene, under Elevated Temperature Conditions
It is stirred at reflux, add in 8.0mL mass concentrations into reaction system when rising to 80 DEG C continues to stir for 30% hydrogen peroxide and 80 DEG C
Flow back 3h, makes reaction system cooled to room temperature, adds in the benzaldehyde in toluene extraction reaction system, is filtered to remove solid and urges
Filtrate rectifying is obtained benzaldehyde by agent.
The catalytic effect analysis of 1 benzaldehyde process for catalytic synthesis of embodiment 3-16 and comparative example：
Embodiment 3-16 and 1 step 2 of comparative example catalyze and synthesize benzaldehyde terminate and complete toluene extraction benzaldehyde
Afterwards, organic phase sample is acquired respectively, and gas chromatographic analysis is carried out to sample, calculates the conversion of styrene respectively using equation below
The selectivity of rate and benzaldehyde：
The conversion ratio calculation formula of benzaldehyde is Con=(n1+n2)/n0× 100%；
The selective calculation formula of benzaldehyde is Sel=n1/(n1+n2) × 100%；
In formula, n0-Put into amount, the n of the substance of styrene1-Generate amount, the n of the substance of benzaldehyde2-Generate the object of benzoic acid
The amount of matter；
The results are shown in Table 1：
Table 1
| Test item | The conversion ratio (%) of styrene | The selectivity (%) of benzaldehyde |
| Embodiment 3 | 44.32 | 95.73 |
| Embodiment 4 | 47.04 | 94.21 |
| Embodiment 5 | 50.8 | 90.84 |
| Embodiment 6 | 53.5 | 87.1 |
| Embodiment 7 | 45.72 | 92.7 |
| Embodiment 8 | 61.3 | 79.5 |
| Embodiment 9 | 60.8 | 80.4 |
| Embodiment 10 | 50.6 | 93.8 |
| Embodiment 11 | 40.5 | 95.6 |
| Embodiment 12 | 43.9 | 95.7 |
| Embodiment 13 | 44.3 | 100 |
| Embodiment 14 | 42.1 | 94.6 |
| Embodiment 15 | 58.9 | 80.23 |
| Embodiment 16 | 48.8 | 91.8 |
| Comparative example 1 | 36.2 | 66.26 |
Using different it can be seen from the styrene conversion rate of embodiment 3-16 in table 1 and the selective data of benzaldehyde
Catalyst calcination temperature, difference ZrO2With NH4VO3Mass ratio and the SO for preparing of different sulfuric acid concentration4 2-/V2O5-ZrO2It is compound
The conversion ratio of catalyst styrene reaches as high as 61.3% more than 40%；The selectivity of benzaldehyde 70% with
On, wherein by 10 embodiments more than 90%, highest benzaldehyde is selectively 100%.And SO prepared by comparative example 14 2-/-
ZrO2The styrene catalyzed conversion ratio of composite catalyst is only 36.2%, and benzaldehyde is only selectively 66.26%, it is possible thereby to see
Go out V in composite catalyst2O5Introducing stabilize ZrO2Crystalline phase, improve SO4 2-Decomposition temperature, enhance the steady of catalyst
It is qualitative, so as to make SO4 2-/V2O5-ZrO2Composite catalyst has higher than SO4 2-/-ZrO2The catalytic activity of composite catalyst.
Prepare SO4 2-/V2O5-ZrO2The optimum condition of composite catalyst is 500 DEG C of calcination temperature, ZrO2And NH4VO 3Matter
Amount is than being 1:1, sulfuric acid concentration 23%.
Fig. 1 be embodiment 13 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram；Figure
The peak occurred at middle 2.993min is the peak of toluene, and peak area 1254997.1, the peak occurred at 3.787min is styrene
Peak, peak area 95203.3, at 4.471min occur peak be product benzaldehyde peak, peak area 39542.6.
Fig. 2 be embodiment 15 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram；Figure
The peak occurred at middle 3.061min is the peak of toluene, and peak area 2292175.3, the peak occurred at 3.914min is styrene
Peak, peak area 42015.9, peak of the peak occurred at 4.503min for product benzaldehyde, peak area 39520.4.
Fig. 3 be embodiment 16 catalyze and synthesize benzaldehyde after reaction toluene extraction organic phase gas chromatogram；Figure
The peak occurred at middle 3.02min is the peak of toluene, and peak area 1639356.5, the peak occurred at 3.857min is styrene
Peak, peak area 241495.5, at 4.477min occur peak be product benzaldehyde peak, peak area 34905.5.
Claims (9)
1. a kind of process for catalytic synthesis of benzaldehyde, it is characterised in that the process for catalytic synthesis step is as follows：
Step 1: prepare SO4 2-/V2O5-ZrO2Composite catalyst：
By certain mass than ZrO2And NH4VO3It is added in the sulfuric acid solution of certain mass concentration, completes at a certain temperature
It is stirred at reflux, decompression filters and obtains solid product, and the solid product is washed to neutrality and after drying, is placed under certain temperature
It is roasted, obtains SO4 2-/V2O5-ZrO2Composite catalyst；
Step 2: catalyze and synthesize benzaldehyde：
The SO as made from certain mass volume ratio gets step 1 ready4 2-/V2O5-ZrO2Composite catalyst, styrene and hydrogen peroxide, will
SO4 2-/V2O5-ZrO2Composite catalyst is added in styrene, is stirred at reflux under Elevated Temperature Conditions, to anti-when rising to certain temperature
It answers and hydrogen peroxide is added in system and the temperature is kept to continue to be stirred at reflux after a certain period of time, reaction system is made to naturally cool to room
Temperature adds in the benzaldehyde in toluene extraction reaction system, is filtered to remove solid catalyst, filtrate rectifying is obtained benzaldehyde.
A kind of 2. process for catalytic synthesis of benzaldehyde according to claim 1, it is characterised in that ZrO described in step 12With
NH4VO3Mass ratio be 1:0.1~2, the mass concentration of the sulfuric acid solution is 5~50%, and the temperature that is stirred at reflux is 20
~30 DEG C, the time is stirred at reflux as 10~20h.
A kind of 3. process for catalytic synthesis of benzaldehyde according to claim 1 or claim 2, it is characterised in that ZrO described in step 12With
NH4VO3Mass ratio be 1:0.6~1.4g, the mass concentration of the sulfuric acid solution is 9~33%.
A kind of 4. process for catalytic synthesis of benzaldehyde according to claim 3, it is characterised in that drying condition described in step 1
For 100~150 DEG C of dry 5~10h.
A kind of 5. process for catalytic synthesis of benzaldehyde according to claim 4, it is characterised in that roasting condition described in step 1
1~5h is roasted for 400~900 DEG C of Muffle furnaces.
A kind of 6. process for catalytic synthesis of benzaldehyde according to claim 5, it is characterised in that roasting condition described in step 1
It is 400~600 DEG C.
A kind of 7. process for catalytic synthesis of benzaldehyde according to claim 6, it is characterised in that SO described in step 24 2-/V2O5-
ZrO2The mass volume ratio of composite catalyst, styrene and hydrogen peroxide is (0.1~0.5) g：(1~5) mL：(1~10) mL.
8. a kind of process for catalytic synthesis of benzaldehyde according to claim 7, it is characterised in that dioxygen is added in described in step 2
The temperature of reaction system is 50~100 DEG C during water, and the hydrogen peroxide mass concentration is 30%.
A kind of 9. process for catalytic synthesis of benzaldehyde according to claim 8, it is characterised in that reaction system described in step 2
Continue the time being stirred at reflux as 3~9h after adding in hydrogen peroxide.
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| CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
| 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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| CN111170838A (en) * | 2020-01-14 | 2020-05-19 | 中北大学 | Method and reaction device for preparing benzaldehyde by supergravity ozone oxidation of styrene |
| CN111170838B (en) * | 2020-01-14 | 2023-04-14 | 中北大学 | Method and reaction device for preparing benzaldehyde by supergravity ozone oxidation of styrene |
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