CN107805190A - A kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system - Google Patents
A kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system Download PDFInfo
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- CN107805190A CN107805190A CN201711082873.1A CN201711082873A CN107805190A CN 107805190 A CN107805190 A CN 107805190A CN 201711082873 A CN201711082873 A CN 201711082873A CN 107805190 A CN107805190 A CN 107805190A
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- phenmethylol
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- catalyst
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- benzaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
The invention provides a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system, including according to quality parts ratio, the step of weighing catalyst and phenmethylol；Catalyst and phenmethylol are added into reactor, seal reactor, and be stirred so that react abundant step.The present invention realizes phenmethylol direct oxidation producing benzaldehyde with high selectivity, more efficiently facilitates the conversion of phenmethylol and the generation of benzaldehyde in the absence of a solvent by the use of atmospheric air as oxygen source, activated carbon supported nano cupric oxide as catalyst.Meanwhile catalyst is still after the reaction solid, facilitates utilization and recycle.
Description
Technical field
The present invention relates to the method for preparing benzaldehyde, and in particular to a kind of air oxidation phenmethylol benzene of solvent-free system
The method of formaldehyde.
Background technology
Aromatic aldehyde is a kind of important organic chemical industry's intermediate, is mainly used in the industries such as medicine, plastics, additive, spices,
Therefore, it is very important organic reaction that aromatic alcohol, which is oxidized to corresponding aromatic aldehyde,.However, because peroxide easily occurs for aromatic aldehyde
Change reaction generation carboxylic acid, cause aromatic alcohol to be oxidized to the selectivity of aromatic aldehyde and substantially reduce, the serious yield for restricting aromatic aldehyde.Closely
Nian Lai, Many researchers using transition-metal catalyst come improve benzyl alcohol oxidation be benzaldehyde selectivity, obtain well into
Effect, but still restricted by each side, such as：Catalyst and organic solvent cost are high and are not environment friendly type material, catalyst
Easy in inactivation, separation difficulty etc..
At present, industrial generally use chlorination toluene Hydrolyze method production benzaldehyde.Technological process length, product be present in this method
Separation is difficult, discharges the defects of corrosive gas and debirs, and chloride or chlorion are contained particularly in benzaldehyde product,
The serious application for limiting benzaldehyde in medicine and spices.Therefore exploitation is composite green chemistry without chlorine technical process and can held
The important research direction of supervention exhibition.
Oxybenzene methyl alcohol producing benzaldehyde is the important reaction studied both at home and abroad.The reaction system reported is more using organic molten
Agent, either pure oxygen be oxidant or use noble metal these are all unfavorable for follow-up practical application as catalyst.For example,
Watanabe（ACS Catal. 2015, 5:2886-2894）It is catalyst to report the activated carbon mixed with nitrogen, and pure oxygen is oxygen
Agent, ethanol are solvent, and 120 °C, reaction time 5h of reaction temperature, the yield of benzaldehyde is 23%, is selectively>99%.This is anti-
Answer system to need to use organic solvent ethanol, add the cost of subsequent products separation.Huang（Green Chem., 2015,
17: 2325-2329）The gold nano grain supported with ionic liquid-polyoxometallate is catalyst, is solvent with water, normal pressure
Air, which is bubbled into system, is used as oxidant, under 75 °C and 3h of reaction condition, can obtain 99% benzaldehyde yield
（Based on 1 mmol phenmethylols）.This reaction system needs to use expensive ionic liquid and noble metal gold, adds cost,
There is an urgent need to improved.
The content of the invention
To solve the above problems, the invention provides a kind of side of the air oxidation phenmethylol producing benzaldehyde of solvent-free system
Method, it is real in the absence of a solvent as catalyst by the use of atmospheric air as oxygen source, activated carbon supported nano cupric oxide
Show phenmethylol direct oxidation producing benzaldehyde with high selectivity, more efficiently facilitate the conversion of phenmethylol and the generation of benzaldehyde.Meanwhile
Catalyst is still after the reaction solid, facilitates utilization and recycle.
To realize the technical purpose, the technical scheme is that：A kind of air oxidation phenmethylol of solvent-free system
The method of producing benzaldehyde, comprises the following steps：S1：According to quality parts ratio, catalyst and phenmethylol are weighed；S2：By step S1
In catalyst and phenmethylol add into reactor, seal reactor, and be stirred so that reaction is abundant.
Further, the quality parts ratio of catalyst and phenmethylol is 1 in the step S1:9~1:27.
Further, catalyst is activated carbon supported nano cupric oxide in the step S1.
Further, the particle diameter of cupric oxide is 20 rans in the activated carbon supported nano cupric oxide, and cupric oxide
Load capacity on the activated carbon is 1%-4%.
Further, the preparation method of the activated carbon supported nano cupric oxide, comprises the following steps：
T1：Copper acetate dihydrate is dissolved in deionized water, adds glacial acetic acid, and stir；T2：Activated carbon is added, and is surpassed
Sonication and heating；T3：Sodium hydrate aqueous solution is added dropwise dropwise；T4：After reaction fully, cooling, filter, wash three times；T5：Drum
Air-dry dry.
As a preference of the present invention, the reactor in the step S2 is pressure-resistant reaction bulb.
Further, atmospheric air is led in the pressure-resistant reaction bulb.
Further, the reaction temperature in the step S2 is 120-150 °C.
Further, the reflecting time in the step S2 is 4-6h.
The beneficial effects of the present invention are：
1）, the present invention preparation method, using atmospheric air as oxidant, without cost, environmental sound；
2), the catalyst used in preparation method of the invention is free of noble metal, and cost is relatively low, and preparation method is simple, urges
Change stable performance；
3）, the present invention preparation method in reaction system without using organic solvent, reduce the cost of later separation；
4）, the present invention preparation method in benzaldehyde high income up to 71.2%, benzaldehyde selectivity>99%（Analyzed based on GC
As a result）.
5）, the present invention preparation method in catalyst be solid after the completion of reaction, convenient recovery reuse.
To sum up：The present invention is by the use of atmospheric air as oxygen source, and activated carbon supported nano cupric oxide is as catalyst, in nothing
Phenmethylol direct oxidation producing benzaldehyde with high selectivity is realized under conditions of solvent, more efficiently facilitates conversion and the benzene first of phenmethylol
The generation of aldehyde.Meanwhile catalyst is still after the reaction solid, facilitates utilization and recycle.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of catalyst of the present invention.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below.Obviously, described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
A kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system, comprises the following steps：S1：According to quality
Portion rate, weigh catalyst and phenmethylol；S2：Catalyst in step S1 and phenmethylol are added into reactor, sealing is anti-
Device is answered, and is stirred so that reaction is abundant.
Further, the quality parts ratio of catalyst and phenmethylol is 1 in the step S1:9~1:27.
Further, catalyst is activated carbon supported nano cupric oxide in the step S1.
Further, the particle diameter of cupric oxide is 20 rans in the activated carbon supported nano cupric oxide, and cupric oxide
Load capacity on the activated carbon is 1%-4%.
Further, the preparation method of the activated carbon supported nano cupric oxide, comprises the following steps：
T1：Copper acetate dihydrate is dissolved in deionized water, adds glacial acetic acid, and stir；T2：Activated carbon is added, and is surpassed
Sonication and heating；As a kind of preferred embodiment of the present invention, commercial activated carbons C can be selected in activated carbon（Chinese medicines group
Chemical reagent Co., Ltd, analysis are pure）.T3：Sodium hydrate aqueous solution is added dropwise dropwise；T4：After reaction fully, cooling, filter, water
Wash three times；T5：Forced air drying.
As a kind of embodiment of the present invention, with the CuO-C of 2% load capacity（Activated carbon supported nano cupric oxide）Exemplified by,
Its preparation method is：T1：0.1 g copper acetate dihydrates, are dissolved in 25 mL deionized water, add 125 μ L glacial acetic acid,
It is stirred at room temperature 10 minutes.T2：2.5 g C are added, ultrasound 30 minutes, are heated to 90 DEG C.T3：It is added dropwise dropwise thereto and adds 1.5 mL
Sodium hydrate aqueous solution（0.125 g sodium hydroxides are dissolved in 1.5 mL deionized waters）.T4：Reaction stops anti-after 20 minutes
Should, cool down, filter, washing is three times.T5：100 DEG C of forced air dryings 12 hours.Scanning electron microscopy after the completion of catalyst preparation
Mirror（SEM）As shown in Figure 1.
As a preference of the present invention, the reactor in the step S2 is pressure-resistant reaction bulb.
Further, atmospheric air is led in the pressure-resistant reaction bulb.
Further, the reaction temperature in the step S2 is 120-150 °C.
Further, the reflecting time in the step S2 is 4-6h.
A kind of embodiment preferentially selected as the present invention：By the substrate benzene first of the catalyst of precise and 5mmol
Alcohol is successively added in the pressure-resistant reaction bulbs of 100 mL, tightens bottle cap, opens stirring, is started when temperature rises to 120-150 °C anti-
Should, stop reaction after 4-6h；Benzaldehyde yield is analyzed with gas chromatograph GC.
Different quality containing is explained below than, the experiment knot under the conditions of catalyst cupric oxide load capacity, reaction temperature etc.
Fruit：Experiment 1：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 1%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 140 DEG C, the yield of benzaldehyde is 52.6%, selectivity
>99%。
Experiment 2：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 4%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 140 DEG C, the yield of benzaldehyde is 70%, is selectively
90%, accessory substance is a small amount of benzoic acid.
Experiment 3：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 120 DEG C, the yield of benzaldehyde is 22.6%, selectivity
>99%。
Experiment 4：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 150 DEG C, the yield of benzaldehyde is 65%, is selectively
87%, accessory substance is a small amount of benzoic acid.
Experiment 5：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 4 h at 140 DEG C, the yield of benzaldehyde is 45.5%, selectivity
>99%。
Experiment 6：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 6 h at 140 DEG C, the yield of benzaldehyde is 67.3%, selectivity
For 94%, accessory substance is a small amount of benzoic acid.
Experiment 7：
Into the pressure-resistant reaction bulbs of 100 mL, 0.02 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 140 DEG C, the yield of benzaldehyde is 37.1%, selectivity
>99%。
Experiment 8：
Into the pressure-resistant reaction bulbs of 100 mL, 0.06 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 140 DEG C, the yield of benzaldehyde is 70.4%, selectivity
For 98%, accessory substance is a small amount of benzoic acid.
Experiment 9：
Into the pressure-resistant reaction bulbs of 100 mL, 0.05 g catalyst CuO-C of precise is added（Load capacity is 2%）, add substrate
The g of phenmethylol 0.54（5 mmol）, reacted, reacted after 5 h at 140 DEG C, the yield of benzaldehyde is 71.2%, selectivity
>99%。
To sum up, the method that the present invention prepares benzaldehyde, its method for preparing catalyst is simple, stable in catalytic performance；And react
System is low without using organic solvent, later separation cost；The high income that benzaldehyde is can be seen that based on GC analysis results is reached
71.2%, benzaldehyde selectivity>99%.It is solid after the completion of reaction to test reacted catalyst above, convenient recovery weight
It is multiple to use.
For the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also do
Go out several modifications and improvements, these belong to protection scope of the present invention.
Claims (9)
1. the method for the air oxidation phenmethylol producing benzaldehyde of a kind of solvent-free system, it is characterised in that comprise the following steps：
S1：According to quality parts ratio, catalyst and phenmethylol are weighed；S2：Catalyst in step S1 and phenmethylol are added to reaction
In device, reactor is sealed, and be stirred so that reaction is abundant.
2. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 1, its feature
It is, the quality parts ratio of catalyst and phenmethylol is 1 in the step S1:9~1:27.
3. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 1, its feature
It is, catalyst is activated carbon supported nano cupric oxide in the step S1.
4. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 3, its feature
It is, the particle diameter of cupric oxide is 20 rans in the activated carbon supported nano cupric oxide, and cupric oxide is on the activated carbon
Load capacity be 1%-4%.
5. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 3, its feature
It is, the preparation method of the activated carbon supported nano cupric oxide, comprises the following steps：
T1：Copper acetate dihydrate is dissolved in deionized water, adds glacial acetic acid, and stir；T2：Activated carbon is added, and is surpassed
Sonication and heating；T3：Sodium hydrate aqueous solution is added dropwise dropwise；T4：After reaction fully, cooling, filter, wash three times；T5：Drum
Air-dry dry.
6. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 1, its feature
It is, the reactor in the step S2 is pressure-resistant reaction bulb.
7. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 6, its feature
It is, atmospheric air is led in the pressure-resistant reaction bulb.
8. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 1, its feature
It is, the reaction temperature in the step S2 is 120-150 °C.
9. a kind of method of the air oxidation phenmethylol producing benzaldehyde of solvent-free system according to claim 1, its feature
It is, the reflecting time in the step S2 is 4-6h.
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| CN201711082873.1A CN107805190B (en) | 2017-11-07 | 2017-11-07 | Method for preparing benzaldehyde by air oxidation of benzyl alcohol without solvent system |
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| CN201711082873.1A CN107805190B (en) | 2017-11-07 | 2017-11-07 | Method for preparing benzaldehyde by air oxidation of benzyl alcohol without solvent system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607557A (en) * | 2018-05-22 | 2018-10-02 | 常州大学 | A kind of preparation method and application of copper oxide clay |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193600A (en) * | 2014-08-11 | 2014-12-10 | 济南大学 | Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193600A (en) * | 2014-08-11 | 2014-12-10 | 济南大学 | Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst |
Non-Patent Citations (2)
| Title |
|---|
| RAJU POREDDY ET AL: "Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air", 《CATALYSIS SCIENCE& TECHNOLOGY》 * |
| 华鹏飞: "活性炭负载金属催化剂的研究进展", 《当代化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607557A (en) * | 2018-05-22 | 2018-10-02 | 常州大学 | A kind of preparation method and application of copper oxide clay |
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