CN102503768A - Method for selectively oxidizing toluene in water - Google Patents
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Abstract
The invention relates to a method for selectively oxidizing toluene in water. HZSM-5, NaZSM-5 or hydrogen-type beta molecular sieves are used as a catalyst, hydrogen peroxide is used as an oxidant, and water is used as a reaction solvent, and can realize toluene oxidation at a lower temperature to mainly produce benzaldehyde, benzyl alcohol, benzoic acid and phenols. By treating the HZSM-5 and NaZSM-5 molecular sieves with alkali solution, catalyst activity can be further improved. Compared with a conventional reaction system, the oxidation reaction system adopts water as a reaction solvent instead of an organic solvent, by-product esters production is greatly reduced and the production cost is reduced. Reaction is controlled at a relatively low temperature, and deep oxidation reaction and carbon deposition can be effectively limited. The system is a green high-efficiency oxidation reaction system and has a very good application prospect in industrial production.
Description
Technical field
The invention belongs to field of catalytic reactions, relate to a kind of in water the method for selective oxidation toluene.
Background technology
Oxidation toluene can obtain important chemical material such as phenyl aldehyde, phenylcarbinol and phenylformic acid, and is the focus of research and development in recent years with oxygen as oxygen source oxidation toluene.Patent CN1068755 discloses and a kind ofly makes the toluene catalytic gas phase oxidation to produce the catalyzer of phenyl aldehyde with air.Its technical scheme is in vanadic acid silver, to add nickel, and adds the thulium cerium again with the preparation catalyzer.Use this catalyzer, the per pass conversion of toluene can reach 10-53%, and the selectivity of phenyl aldehyde is 60-30%.Owing in reaction, do not use water vapour, reduced production cost.Patent CN1296937, relate to a kind of in liquid phase oxidation toluene prepare phenyl aldehyde, phenylcarbinol and benzoic method; Its scheme be monoalkylated benzenes compound and oxygen-containing gas with cobalt salt or the catalysis of cobalt salt manganese addition salt, oxidizing reaction temperature is 130-200 ℃, pressure is 0.3-0.8MPa; Oxidation 1-8 hour; The phenyl aldehyde productive rate can reach more than 20%, and the phenylcarbinol productive rate is more than 10%, and the phenylformic acid productive rate is more than 60%.Except that using cobalt salt or cobalt salt manganese addition salt to do the catalyzer, also need use metal-salt to make co-catalyst in the reaction, bromide is made promotor, and phenyl aldehyde is made initiator.In addition, patent US3387036, CN1485131 etc. all relate to the toluene liquid phase oxidation reaction.These disclosed liquid-phase oxidation toluene technology have following characteristics: 1. adopt organism to make reaction solvent, for example: peruscabin (CN101786974), organic acid etc. mostly; 2. make catalyzer with metal-salt, contain heavy metal, for example: cobalt, silver, vanadium etc.; 3. wait with promotor, promotor, initiator and improve reactive behavior; 4. oxygen-containing gas is made oxygenant and is needed control pressure.Simultaneously, also there are some problems in these liquid-phase oxidation toluene technology, and for example: catalyzer is formed complicated; The use of heavy metal and heavy metallic salt can produce heavy metal ion, pollutes; Reactor drum is had relatively high expectations etc.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of in water the method for selective oxidation toluene.This method is different from traditional liquid-phase oxidation, and this oxidizing reaction system is compared with traditional reaction system, adopts water to replace organic reagent to make reaction solvent, has significantly reduced the generation of by product ester class, and has reduced production cost.
The present invention realizes through following technical scheme:
A kind of in water the method for selective oxidation toluene, this method may further comprise the steps: get the 0.075-5.0g catalyzer, 2.0-24.0ml toluene joins in the 2.0-400ml water, is warming up to 40-100 ℃, is added dropwise to the 2.0-180ml ydrogen peroxide 50, reaction 0.2-10h; Reaction product is used ethyl acetate extraction.
And described catalyzer is HZSM-5 or the NaZSM-5 after the alkaline purification after HZSM-5 or NaZSM-5 or Hydrogen beta-molecular sieve or the alkaline purification.
And, the silica alumina ratio (SiO of described HZSM-5 or NaZSM-5
2/ Al
2O
3) be 25-100, the silica alumina ratio (SiO of Hydrogen beta-molecular sieve
2/ Al
2O
3) be 25.
And the method for alkaline purification HZSM-5 or NaZSM-5 may further comprise the steps: get 4.0-20gHZSM-5 or NaZSM-5 molecular sieve, join in the 0.1-1.0LNaOH solution; The NaOH strength of solution is 0-0.4mol/L; Under 0-100 ℃, stir 80-240min, suction filtration; Drying promptly gets HZSM-5 or the NaZSM-5 after the alkaline purification after the alkaline purification.
Advantage of the present invention and beneficial effect are:
1. make reaction solvent with water to replace organic solvent, reduced cost, and can suppress the generation of some by product;
2. sieve peg-raking catalyst makes that catalyzer is easy to separate, and reclaims; Catalyzer is stable in reaction system, can repeatedly recycle, and catalytic activity does not have obvious reduction; Catalyzer is convenient to store transportation;
3. be reflected under the normal pressure and can take place, the low generation that can reduce the deep oxidation product of temperature of reaction effectively avoids generating carbon distribution, has prolonged the work-ing life of catalyzer;
4. reaction system is not introduced heavy metal, can not produce the waste liquid that contains heavy metal ion, has reduced the use of organic reagent in the reaction, has significantly reduced environmental pollution.
5. the reaction times lacks, to phenyl aldehyde, and phenylcarbinol, the selectivity of important products such as phenylformic acid and phenols is high; Because ydrogen peroxide 50 as oxygenant, phenols occurred in the product, be different from the toluene oxidation reaction system that traditional use oxygen-containing gas is made oxygenant, and the ortho-cresol productive rate is higher.Ortho-cresol is one of three kinds of important source material of preparation " lysol ".
In a word, aqueous phase oxidation toluene is a kind of method of new selective oxidation toluene, can generate multiple important organism, and selectivity is high, and employed catalyzer is a kind of eco-friendly heterogeneous catalyst, and favorable industrial application prospect is arranged.
Embodiment
The present invention further details through following examples, but the technology contents that present embodiment is narrated is illustrative, rather than determinate, should not limit to protection scope of the present invention according to this.
Embodiment 1
Without the HZSM-5 molecular sieve (silica alumina ratio is 25) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.10g catalyzer, 2.0ml toluene joins in the 25ml water, is warming up to 100 ℃, is added dropwise to the 10ml ydrogen peroxide 50, reaction 8h; Reaction product is used ethyl acetate extraction.Toluene conversion is 8.2%, phenyl aldehyde selectivity 32.5%, and benzyl alcohol selective is 19.4%, and the phenylformic acid selectivity is 27.1%, and the ortho-cresol selectivity is 17.3%.
Embodiment 2
Get 4.0g HZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.1LNaOH solution, the NaOH strength of solution is 0mol/L, under 100 ℃, stirs 240min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.075g catalyzer, 2.0ml toluene joins in the 2.0ml water, is warming up to 94 ℃, is added dropwise to the 2.0ml ydrogen peroxide 50, reaction 10h; Reaction product is used ethyl acetate extraction.Toluene conversion is 11.9%, and the phenyl aldehyde selectivity is 18.1%, and benzyl alcohol selective is 17.2%, and the phenylformic acid selectivity is 24.8%, and the ortho-cresol selectivity is 26.9%.
Embodiment 3
Get 20g HZSM-5 molecular sieve (silica alumina ratio is 25), join in the 1.0LNaOH solution, the NaOH strength of solution is 0.4mol/L, under 0 ℃, stirs 120min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.20g catalyzer, 2.0ml toluene joins in the 25ml water, is warming up to 94 ℃, is added dropwise to the 8.0ml ydrogen peroxide 50, reaction 3h; Reaction product is used ethyl acetate extraction.Toluene conversion is 6.3%, and the phenyl aldehyde selectivity is 48.4%, and benzyl alcohol selective is 24.3%, and the phenylformic acid selectivity is 11.3%, and the ortho-cresol selectivity is 8.9%.
Embodiment 4
Get 10g HZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.3LNaOH solution, the NaOH strength of solution is 0.2mol/L, under 60 ℃, stirs 180min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 5.0g catalyzer, 24.0ml toluene joins in the 400ml water, is warming up to 100 ℃, is added dropwise to the 180.0ml ydrogen peroxide 50, reaction 7h; Reaction product is used ethyl acetate extraction.Toluene conversion is 27.3%, and the phenyl aldehyde selectivity is 28.1%, and benzyl alcohol selective is 23.3%, and the phenylformic acid selectivity is 21.6%, and the ortho-cresol selectivity is 20.4%.
Embodiment 5
Get 4.0g HZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.LNaOH solution, the NaOH strength of solution is 0.2mol/L, under 80 ℃, stirs 120min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.125g catalyzer, 2.0ml toluene joins in the 24ml water, is warming up to 40 ℃, is added dropwise to the 8.0ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 7.3%, and the phenyl aldehyde selectivity is 61.9%, and benzyl alcohol selective is 23.6%, and the phenylformic acid selectivity is 6.6%, and the ortho-cresol selectivity is 3.5%.
Embodiment 6
Get 15g HZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.5LNaOH solution, the NaOH strength of solution is 0.2mol/L, under 80 ℃, stirs 80min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 1.5g catalyzer, 8.0ml toluene joins in the 50ml water, is warming up to 94 ℃, is added dropwise to the 30.0ml ydrogen peroxide 50, reaction 0.2h; Reaction product is used ethyl acetate extraction.Toluene conversion is 6.5%, and the phenyl aldehyde selectivity is 55.6%, and benzyl alcohol selective is 21.9%, and the phenylformic acid selectivity is 6.9%, and the ortho-cresol selectivity is 8.4%.
Embodiment 7
Without the HZSM-5 molecular sieve (silica alumina ratio is 38) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.20g catalyzer, 2.0ml toluene joins in the 60ml water, is warming up to 90 ℃, is added dropwise to the 12.0ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 12.7%, and the phenyl aldehyde selectivity is 21.2%, and benzyl alcohol selective is 21.3%, and the phenylformic acid selectivity is 19.8%, and the ortho-cresol selectivity is 23.4%.
Embodiment 8
Without the HZSM-5 molecular sieve (silica alumina ratio is 100) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.8g catalyzer, 2.0ml toluene joins in the 30ml water, is warming up to 80 ℃, is added dropwise to the 20.0ml ydrogen peroxide 50, reaction 6h; Reaction product is used ethyl acetate extraction.Toluene conversion is 14.1%, and the phenyl aldehyde selectivity is 36.4%, and benzyl alcohol selective is 26.8%, and the phenylformic acid selectivity is 13.4%, and the ortho-cresol selectivity is 21.1%.
Embodiment 9
Get 12g HZSM-5 molecular sieve (silica alumina ratio is 38), join in the 1.0LNaOH solution, the NaOH strength of solution is 0.1mol/L, under 80 ℃, stirs 120min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 1.0g catalyzer, 8.0ml toluene joins in the 60ml water, is warming up to 94 ℃, is added dropwise to the 60ml ydrogen peroxide 50, reaction 4h; Reaction product is used ethyl acetate extraction.Toluene conversion is 21.7%, and the phenyl aldehyde selectivity is 33.6%, and benzyl alcohol selective is 25.0%, and the phenylformic acid selectivity is 15.6%, and the ortho-cresol selectivity is 20.6%.
Embodiment 10
Get 20g HZSM-5 molecular sieve (silica alumina ratio is 100), join in the 1.0LNaOH solution, the NaOH strength of solution is 0.2mol/L, under 100 ℃, stirs 100min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 2.0g catalyzer, 12.0ml toluene joins in the 80ml water, is warming up to 80 ℃, is added dropwise to the 120ml ydrogen peroxide 50, reaction 6h; Reaction product is used ethyl acetate extraction.Toluene conversion is 19.0%, and the phenyl aldehyde selectivity is 26.0%, and benzyl alcohol selective is 23.8%, and the phenylformic acid selectivity is 24.4%, and the ortho-cresol selectivity is 18.8%.
Embodiment 11
Without the NaZSM-5 molecular sieve (silica alumina ratio is 25) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.125g catalyzer, 2.0ml toluene joins in the 24ml water, is warming up to 94 ℃, is added dropwise to the 8.0ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 16.2%, and the phenyl aldehyde selectivity is 38.1%, and benzyl alcohol selective is 22.8%, and the phenylformic acid selectivity is 9.0%, and the ortho-cresol selectivity is 26.7%.
Embodiment 12
Get 4.0g NaZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.1LNaOH solution, the NaOH strength of solution is 0mol/L, under 75 ℃, stirs 180min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.075g catalyzer, 2.0ml toluene joins in the 2.0ml water, is warming up to 100 ℃, is added dropwise to the 2.0ml ydrogen peroxide 50, reaction 10h; Reaction product is used ethyl acetate extraction.Toluene conversion is 15.0%, and the phenyl aldehyde selectivity is 23.4%, and benzyl alcohol selective is 14.0%, and the phenylformic acid selectivity is 25.0%, and the ortho-cresol selectivity is 32.0%.
Embodiment 13
Get 20g NaZSM-5 molecular sieve (silica alumina ratio is 25), join in the 1.0LNaOH solution, the NaOH strength of solution is 0.4mol/L, under 0 ℃, stirs 80min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 5.0g catalyzer, 24.0ml toluene joins in the 400ml water, is warming up to 94 ℃, is added dropwise to the 180ml ydrogen peroxide 50, reaction 1h; Reaction product is used ethyl acetate extraction.Toluene conversion is 15.5%, and the phenyl aldehyde selectivity is 32.6%, and benzyl alcohol selective is 17.5%, and the phenylformic acid selectivity is 16.6%, and the ortho-cresol selectivity is 27.5%.
Embodiment 14
Get 10g NaZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.5LNaOH solution, the NaOH strength of solution is 0.2mol/L, under 100 ℃, stirs 240min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 1.2g catalyzer, 7.0ml toluene joins in the 50ml water, is warming up to 40 ℃, is added dropwise to the 30.0ml ydrogen peroxide 50, reaction 4h; Reaction product is used ethyl acetate extraction.Toluene conversion is 21.6%, and the phenyl aldehyde selectivity is 32.6%, and benzyl alcohol selective is 20.6%, and the phenylformic acid selectivity is 11.0%, and the ortho-cresol selectivity is 31.3%.
Embodiment 15
Get 4.0g NaZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.2LNaOH solution, the NaOH strength of solution is 0.05mol/L, under 40 ℃, stirs 120min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.2g catalyzer, 2.0ml toluene joins in the 50ml water, is warming up to 94 ℃, is added dropwise to the 20.0ml ydrogen peroxide 50, reaction 0.2h; Reaction product is used ethyl acetate extraction.Toluene conversion is 12.4%, and the phenyl aldehyde selectivity is 32.7%, and benzyl alcohol selective is 17.6%, and the phenylformic acid selectivity is 11.8%, and the ortho-cresol selectivity is 32.4%.
Embodiment 16
Get 15g NaZSM-5 molecular sieve (silica alumina ratio is 25), join in the 0.5LNaOH solution, the NaOH strength of solution is 0.1mol/L, under 60 ℃, stirs 80min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.9g catalyzer, 8.0ml toluene joins in the 80ml water, is warming up to 80 ℃, is added dropwise to the 25.0ml ydrogen peroxide 50, reaction 6h; Reaction product is used ethyl acetate extraction.Toluene conversion is 23.3%, and the phenyl aldehyde selectivity is 31.1%, and benzyl alcohol selective is 20.1%, and the phenylformic acid selectivity is 14.9%, and the ortho-cresol selectivity is 29.9%.
Embodiment 17
Without the NaZSM-5 molecular sieve (silica alumina ratio is 38) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.3g catalyzer, 4.0ml toluene joins in the 40ml water, is warming up to 100 ℃, is added dropwise to the 10.0ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 19.8%, and the phenyl aldehyde selectivity is 32.2%, and benzyl alcohol selective is 19.1%, and the phenylformic acid selectivity is 17.1%, and the ortho-cresol selectivity is 26.0%.
Embodiment 18
Without the NaZSM-5 molecular sieve (silica alumina ratio is 100) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.5g catalyzer, 2.0ml toluene joins in the 30ml water, is warming up to 60 ℃, is added dropwise to the 20.0ml ydrogen peroxide 50, reaction 8h; Reaction product is used ethyl acetate extraction.Toluene conversion is 5.9%, and the phenyl aldehyde selectivity is 52.4%, and benzyl alcohol selective is 22.9%, and the phenylformic acid selectivity is 3.3%, and the ortho-cresol selectivity is 14.6%.
Embodiment 19
Get 12g NaZSM-5 molecular sieve (silica alumina ratio is 38), join in the 0.4LNaOH solution, the NaOH strength of solution is 0.1mol/L, under 60 ℃, stirs 120min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 1.0g catalyzer, 6.0ml toluene joins in the 60ml water, is warming up to 90 ℃, is added dropwise to the 40.0ml ydrogen peroxide 50, reaction 4h; Reaction product is used ethyl acetate extraction.Toluene conversion is 23.3%, and the phenyl aldehyde selectivity is 31.1%, and benzyl alcohol selective is 20.1%, and the phenylformic acid selectivity is 14.9%, and the ortho-cresol selectivity is 29.9%.
Embodiment 20
Get 20g NaZSM-5 molecular sieve (silica alumina ratio is 100), join in the 1.0LNaOH solution, the NaOH strength of solution is 0.05mol/L, under 100 ℃, stirs 100min, suction filtration, drying.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 1.4g catalyzer, 12.0ml toluene joins in the 80ml water, is warming up to 94 ℃, is added dropwise to the 100ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 17.6%, and the phenyl aldehyde selectivity is 26.6%, and benzyl alcohol selective is 16.7%, and the phenylformic acid selectivity is 14.9%, and the ortho-cresol selectivity is 38.5%.
Embodiment 21
Without the Hydrogen beta-molecular sieve (silica alumina ratio is 25) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 2.0g catalyzer, 12.0ml toluene joins in the 80ml water, is warming up to backflow (about 94 ℃), is added dropwise to the 100ml ydrogen peroxide 50, reaction 5h; Reaction product is used ethyl acetate extraction.Toluene conversion is 6.7%, and the phenyl aldehyde selectivity is 45.2%, and benzyl alcohol selective is 19.6%, and the phenylformic acid selectivity is 12.6%, and the ortho-cresol selectivity is 16.1%.
Embodiment 22
Without the Hydrogen beta-molecular sieve (silica alumina ratio is 25) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 0.075g catalyzer, 2.0ml toluene joins in the 2.0ml water, is warming up to 40 ℃, is added dropwise to the 2.0ml ydrogen peroxide 50, reaction 0.2h; Reaction product is used ethyl acetate extraction.Toluene conversion is 5.4%, and the phenyl aldehyde selectivity is 35.1%, and benzyl alcohol selective is 29.3%, and the phenylformic acid selectivity is 0%, and the ortho-cresol selectivity is 30.8%.
Embodiment 23
Without the Hydrogen beta-molecular sieve (silica alumina ratio is 25) of alkaline purification as catalyzer.
Catalytic effect: be reflected in the there-necked flask and carry out, get the 5.0g catalyzer, 24.0ml toluene joins in the 400ml water, is warming up to 100 ℃, is added dropwise to the 180ml ydrogen peroxide 50, reaction 10h; Reaction product is used ethyl acetate extraction.Toluene conversion is 10.5%, and the phenyl aldehyde selectivity is 39.4%, and benzyl alcohol selective is 25.6%, and the phenylformic acid selectivity is 7.6%, and the ortho-cresol selectivity is 25.4%.
Claims (4)
1. the method for a selective oxidation toluene in water, it is characterized in that: this method may further comprise the steps: get the 0.075-5.0g catalyzer, 2.0-24.0ml toluene; Join in the 2.0-400ml water; Be warming up to 40-100 ℃, be added dropwise to the 2.0-180ml ydrogen peroxide 50, reaction 0.2-10h; Reaction product is used ethyl acetate extraction.
2. according to claim 1 in water the method for selective oxidation toluene, it is characterized in that: described catalyzer is HZSM-5 or the NaZSM-5 after the alkaline purification after HZSM-5 or NaZSM-5 or Hydrogen beta-molecular sieve or the alkaline purification.
3. according to claim 1 and 2 in water the method for selective oxidation toluene, it is characterized in that: the silica alumina ratio (SiO of described HZSM-5 or NaZSM-5
2/ Al
2O
3) be 25-100, the silica alumina ratio (SiO of Hydrogen beta-molecular sieve
2/ Al
2O
3) be 25.
4. according to claim 2 in water the method for selective oxidation toluene, it is characterized in that: the method for alkaline purification HZSM-5 or NaZSM-5 may further comprise the steps: get 4.0-20g HZSM-5 or NaZSM-5 molecular sieve, join in the 0.1-1.0LNaOH solution; The NaOH strength of solution is 0-0.4mol/L; Under 0-100 ℃, stir 80-240min, suction filtration; Drying promptly gets HZSM-5 or the NaZSM-5 after the alkaline purification after the alkaline purification.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180836B1 (en) * | 1999-08-17 | 2001-01-30 | National Science Council Of Republic Of China | Preparation of phenol via one-step hydroxylation of benzene catalyzed by copper-containing molecular sieve |
| CN1566052A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing cresol |
| CN101786943A (en) * | 2010-02-25 | 2010-07-28 | 华东理工大学 | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction |
-
2011
- 2011-10-20 CN CN2011103193303A patent/CN102503768A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180836B1 (en) * | 1999-08-17 | 2001-01-30 | National Science Council Of Republic Of China | Preparation of phenol via one-step hydroxylation of benzene catalyzed by copper-containing molecular sieve |
| CN1566052A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing cresol |
| CN101786943A (en) * | 2010-02-25 | 2010-07-28 | 华东理工大学 | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction |
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| Title |
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| PETRE CHIPURICI ET AL.: "Toluen and Benzene Oxidation with Hydrogen Peroxide", 《REV. CHIM.(BUCURESTI)》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
| CN107626349B (en) * | 2017-09-27 | 2020-04-24 | 三峡大学 | Catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid and method for preparing benzyl alcohol, benzaldehyde and benzoic acid |
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Application publication date: 20120620 |