CN107879924A - The synthetic method of benzoic acid under a kind of illumination condition - Google Patents
The synthetic method of benzoic acid under a kind of illumination condition Download PDFInfo
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- CN107879924A CN107879924A CN201711023183.9A CN201711023183A CN107879924A CN 107879924 A CN107879924 A CN 107879924A CN 201711023183 A CN201711023183 A CN 201711023183A CN 107879924 A CN107879924 A CN 107879924A
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- benzoic acid
- toluene
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- illumination condition
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical technology field, the synthetic method of benzoic acid under specially a kind of illumination condition.The inventive method includes：Using toluene as raw material, benzophenone compound is catalyst, without solvent, under the conditions of air at room temperature, reacts 40 48h under visible light illumination, you can efficient to realize that toluene oxidation generates benzoic acid.The inventive method can room temperature and it is solvent-free under the conditions of carry out the photooxidation method of toluene and prepare benzoic acid, realize and the existing production technology of benzoic acid is prepared to toluene oxidation method optimize and transform.The present invention, as catalyst, reduces cost using visible light photosensitizer.The problem of energy consumption can be greatly reduced in the inventive method, and the waste discharge for thoroughly solving the problems, such as to be brought by heavy metal and acetate solvate pollutes heavy-metal residual in environment and product, energy-conserving and environment-protective.The inventive method is compared with traditional production technology, whole power consumption, and equipment investment and overall cost of operation substantially reduce.
Description
Technical field
The invention belongs to chemical technology field, and in particular to the synthetic method of benzoic acid.
Background technology
Benzoic acid is very important basic industries raw material, is widely used in agricultural chemicals, medicine, dyestuff, spices, mordant
And the production of plasticizer, while antirust agent of still conventional food preservative, modifier and steel equipment etc..Benzene first
Acid is very big in international and domestic demand.At present, the technique that the whole world generally prepares benzoic acid using toluene thermal oxidation method.
This method realizes the oxidation of toluene, and finally close by the use of heavy metallic salt cobalt or manganese as catalyst under conditions of HTHP
Into benzoic acid.But this method is always there is high energy consumption, it is seriously polluted the problems such as.
With the proposition of energy-conserving and environment-protective concept, the method for traditional toluene oxidation generation benzoic acid is not more and more by people
Received.
Photochemistry, the science emerging as one, has been obtained for the development of high speed.Compared with traditional heat chemistry, light
Chemistry more clean energy-saving.Therefore, a kind of synthetic method of the benzoic acid under new illumination condition is urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to provide benzene first under a kind of illumination condition for the energy consumption that can reduce environmental pollution, be greatly reduced
The synthetic method of acid.
The synthetic method of benzoic acid under illumination condition provided by the invention, it is the method using organic photochemistry, with toluene
For raw material, benzophenone compound is catalyst, without solvent, room temperature（Such as 10-40 DEG C）, under air conditionses, in visible ray
The lower reaction 40-48h of irradiation, you can efficient to realize that toluene oxidation generates benzoic acid.
The synthetic method of benzoic acid under a kind of illumination condition provided by the present invention, it is characterised in that the synthetic method can
Realize the scale iodine of 5-10 feather weight.
Preferably, in the present invention, described benzophenone compound catalyst is 2- dihydroxy benaophenonels, its structural formula
For：。
Preferably, in the present invention, the dosage of described benzophenone compound is the 1-5% of toluene mass fraction.
Preferably, in the present invention, described light source is 2 1500 W xenon sources.
The principle of the present invention is：2- dihydroxy benaophenonels are changed into excitation state under the irradiation of visible ray from ground state, so as to
Activating catalytic toluene makes it remove a hydrogen atom, generates corresponding benzyl radicalses intermediate, subsequent benzyl radicalses are in sky
Benzaldehyde, the further oxidation by air generation benzoic acid of benzaldehyde are oxidized under the oxidation of gas.
The synthetic method of benzoic acid, has compared with traditional thermochemical processes under a kind of illumination condition provided by the present invention
The advantages of notable：
First, reaction is carried out at ambient temperature, and compared with traditional heating production technology, energy consumption is greatly lowered.
Second, react and carried out under condition of no solvent, so as to solving in traditional handicraft due to making solvent using acetic acid
The all problems brought.Energy consumption is greatly reduced, serious pollution of the spent acid discharge to environment is solved, greatly reduces to equipment
Corrosivity, so as to replace titanium alloy material to manufacture reactor using stainless steel, greatly reduce equipment manufacturing costs.
3rd, using visible light catalyst rather than heavy metal catalyst, so as to thoroughly solve in traditional handicraft due to adopting
Heavy-metal residual problem in problem of environmental pollution, and product caused by with transition-metal catalyst.It means that this method
It is possible to be used directly to produce food even the benzoic acid product of pharmaceutical grade.This will substantially reduce the life of food and medicine level benzoic acid
Produce cost.Moreover, the more traditional toluene thermal oxidation method of catalyst cost decreases.
4th, the present invention uses air as oxidant source, further saves cost.
5th, the present invention post processing it is simple to operation, do not further relate to acetic acid and water separation and heavy metal to environment
Pollution.Acetic acid and heavy metal are free of in caused waste water, can easily carry out integrated treatment, and sensitising agent can reclaim
Utilize.
6th, the raw material that the production method of benzoic acid provided by the present invention uses is single, improves the economy of technique,
And the conversion ratio of toluene, more than 99%, the yield of benzoic acid is more than 97%.
7th, the production method of benzoic acid provided by the present invention, as the energy, without thermal oxide, is located afterwards using visible ray
It is simple to manage equipment, the more existing oxidation production technology of whole power consumption reduces by more than 50%.
8th, the production method of benzoic acid provided by the present invention is without oxidation reaction tower, stripping tower, rectifying column, can be with
Titanium alloy material is replaced using stainless steel to manufacture reactor, the more traditional production technology of equipment investment reduces by more than 30%.
9th, the production method of benzoic acid provided by the present invention is without heavy metal catalyst, without solvent, without oxidation
Reaction tower, without stripping tower, without rectifying column, normal-temperature light can be carried out under shining, and overall cost of operation drops compared with traditional processing technology
Low more than 50%.
In a word, the energy-conserving and environment-protective new technology that this project will develop, thorough solution heavy metal pollution is asked on environmental protection
Topic and spent acid pollution problem；The benzoic acid for being expected to directly produce food and medicine level using this technology is produced in product quality
Product, so as to greatly improve value-added content of product.
Brief description of the drawings
Fig. 1 is benzoic acid nuclear magnetic spectrogram.
Embodiment
Embodiment 1
10kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 2% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 48 h under 2 1500 W xenon source light irradiations.After reaction time reaches, warp
Efficient liquid phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Added in reactant mixture
Sodium hydrate aqueous solution is neutrality to PH, and ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, heavy
Crystallization, vacuum drying, nuclear-magnetism identification, product quality is 13.0 kg, yield 98%.
Embodiment 2
10kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 3% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 46h under 2 1500 W xenon source light irradiations.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality 13.1kg, yield 99%.
Embodiment 3
10kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 4% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 45h under 2 1500 W xenon source light irradiations.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 13.0 kg, yield 98%.
Embodiment 4
10kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 5% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 42h under 2 1500 W xenon source light irradiations.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 13.0 kg, yield 98%.
Embodiment 5
8kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 2% mass fraction, in air atmosphere are added in 50 L reactor
Enclose middle stirring, at a temperature of 25 DEG C, react 48 h under 2 1500 W xenon source light irradiations.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 10.4 kg, yield 98%.
Embodiment 6
8 kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 4% mass fraction, in air are added in 50 L reactor
Stirred in atmosphere, at a temperature of 25 DEG C, react 45h under 2 1500 W xenon source light irradiations.After reaction time reaches, through height
Effect liquid phase chromatogram is analyzed, and the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen is added in reactant mixture
To PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2 aqueous solution of sodium oxide, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 10.4 kg, yield 98%.
Embodiment 7
9kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 3% mass fraction, in air atmosphere are added in 50 L reactor
Enclose middle stirring, at a temperature of 25 DEG C, react 47h under 2 1500 W xenon source light irradiations.After reaction time reaches, through efficient
Liquid-phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen-oxygen is added in reactant mixture
Change sodium water solution to PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 11.7 kg, yield 98%.
Embodiment 8
9kg toluene, the photochemical catalyst 2- dihydroxy benaophenonels of 4% mass fraction, in air atmosphere are added in 50 L reactor
Enclose middle stirring, at a temperature of 25 DEG C, react 45h under 2 1500 W xenon source light irradiations.After reaction time reaches, through efficient
Liquid-phase chromatographic analysis, the generation of only single product benzoic acid, toluene conversion is more than 99%.Hydrogen-oxygen is added in reactant mixture
Change sodium water solution to PH to be neutral, ethyl acetate extraction and recovery sensitising agent, water layer adds watery hydrochloric acid and is adjusted to PH=1-2, ties again
Crystalline substance, vacuum drying, nuclear-magnetism identification, product quality is 11.7 kg, yield 98%.
Claims (4)
- A kind of 1. synthetic method of benzoic acid under illumination condition, it is characterised in that using toluene as raw material, benzophenone compound For catalyst, under room temperature, air conditionses, 40-48h is reacted under visible light illumination, that is, realizes that toluene oxidation generates benzoic acid.
- 2. the synthetic method of benzoic acid under illumination condition according to claim 1, it is characterised in that described hexichol first Ketone compounds catalyst is 2- dihydroxy benaophenonels, and structural formula is： 。
- 3. the synthetic method of benzoic acid under illumination condition according to claim 1, it is characterised in that described benzophenone The dosage of class compound is the 1-5% of toluene mass fraction.
- 4. the synthetic method of benzoic acid under illumination condition according to claim 1, it is characterised in that described light source is 2 The W xenon sources of platform 1500.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210033281A (en) | 2019-09-18 | 2021-03-26 | 한국과학기술연구원 | Method for preparing benzaldehyde |
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| CN1810754A (en) * | 2005-01-27 | 2006-08-02 | 中国科学院化学研究所 | Alkylbenzene photooxidizing process with oxygen to prepare aromatic aldehyde and aromatic acid |
| JP2012056851A (en) * | 2010-09-04 | 2012-03-22 | Nagoya Industrial Science Research Inst | Method for producing aromatic carboxylic acid compound |
| CN103910623A (en) * | 2014-03-03 | 2014-07-09 | 复旦大学 | Preparation method for benzoic acid |
| CN104447271A (en) * | 2014-11-14 | 2015-03-25 | 复旦大学 | Method for synthesizing benzoic acid through alcohol catalysis under condition of illumination |
| CN105061185A (en) * | 2015-07-20 | 2015-11-18 | 复旦大学 | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition |
| CN105152922A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination |
| CN105152905A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid through thioxanthene catalysis under condition of illumination |
-
2017
- 2017-10-26 CN CN201711023183.9A patent/CN107879924A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810754A (en) * | 2005-01-27 | 2006-08-02 | 中国科学院化学研究所 | Alkylbenzene photooxidizing process with oxygen to prepare aromatic aldehyde and aromatic acid |
| JP2012056851A (en) * | 2010-09-04 | 2012-03-22 | Nagoya Industrial Science Research Inst | Method for producing aromatic carboxylic acid compound |
| CN103910623A (en) * | 2014-03-03 | 2014-07-09 | 复旦大学 | Preparation method for benzoic acid |
| CN104447271A (en) * | 2014-11-14 | 2015-03-25 | 复旦大学 | Method for synthesizing benzoic acid through alcohol catalysis under condition of illumination |
| CN105061185A (en) * | 2015-07-20 | 2015-11-18 | 复旦大学 | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition |
| CN105152922A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination |
| CN105152905A (en) * | 2015-07-20 | 2015-12-16 | 复旦大学 | Method for synthesizing benzoic acid through thioxanthene catalysis under condition of illumination |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210033281A (en) | 2019-09-18 | 2021-03-26 | 한국과학기술연구원 | Method for preparing benzaldehyde |
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Application publication date: 20180406 |