CN106565440B - Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction - Google Patents
Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction Download PDFInfo
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- CN106565440B CN106565440B CN201610986937.XA CN201610986937A CN106565440B CN 106565440 B CN106565440 B CN 106565440B CN 201610986937 A CN201610986937 A CN 201610986937A CN 106565440 B CN106565440 B CN 106565440B
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- Prior art keywords
- sulfuric acid
- salt
- benzyl alcohol
- nitrosyl sulfuric
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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
Abstract
The invention discloses application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol.At a lower temperature, salt-free nitrosyl sulfuric acid is added drop-wise in benzyl alcohol solution, is passed through oxygen, is reacted at room temperature, and high conversion and highly selective benzaldehyde are obtained.For the present invention using salt-free nitrosyl sulfuric acid as catalyst, reaction does not consume sulfuric acid.
Description
Technical field
The present invention relates to application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol, specially salt-free nitrosyl sulfuric acid
Catalytic oxygen benzyl alcohol prepares benzaldehyde.
Background technique
Nitrosyl sulfuric acid is a kind of inorganic oxidizer, is mainly used for aoxidizing the reaction that arylamine prepares diazonium salt, and and ring
Hexyl formic acid reaction production caprolactam.
According to the difference of preparation method and ingredient, nitrosyl sulfuric acid, which can be divided into, salt nitrosyl sulfuric acid and salt-free nitrosyl sulfuric acid.
There is salt nitrosyl sulfuric acid to generate nitrosyl sulfuric acid, while the inorganic salts sulphur of the amount of substance such as generation with sodium nitrite and strong sulfuric acid response
Sour hydrogen sodium.Document (Sheng, X.B., et al., Acid-assisted catalytic oxidation of benzyl
alcohol by NOx with dioxygen.Catalysis Communications,2010.11(15):p.1189-
1192.) sodium nitrite and sulfuric acid catalysis Oxybenzene methyl alcohol are used, higher conversion ratio and selectivity are obtained.Due to sodium bisulfate
Solubility in concentrated sulfuric acid is smaller, easily forms crystallization, makes material retrogradation, be unfavorable for reacting, therefore have salt nitrosyl sulfuric acid
Effective concentration is lower, and sulfuric acid consumption is big.Catalytic oxidation of benzyl alcohol after the reaction was completed, catalyst system becomes containing a large amount of sulphur
The sulfuric acid solution of sour hydrogen sodium and sulfuric acid nitrosyl can disappear when supplementing the nitrogen oxide catalyst of reaction escape with sodium nitrite
More sulfuric acid are consumed, more sodium bisulfates are generated, generate more acid solutions, these saliferous acid solutions are difficult to be recycled.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, provides a kind of salt-free nitrosyl sulfuric acid and is catalyzed in benzyl alcohol
Application in oxidation solves the problems, such as that sulfuric acid consumption is big in the prior art.
Technical scheme is as follows:
Application of the salt-free nitrosyl sulfuric acid in the reaction of catalytic phenylmethanol preparing benzaldehyde by oxidizing, specially salt-free nitrosyl
Catalysis oxidation benzyl alcohol prepares benzaldehyde to sulfuric acid in a solvent；The mass ratio of salt-free nitrosyl sulfuric acid and benzyl alcohol is 0.25-1:
1；The volume ratio of solvent and benzyl alcohol is 5-20:1.
The catalytic oxidation temperature is 0-50 DEG C, preferably 5-30 DEG C.
The oxygen pressure of the catalysis oxidation is 0.1-2.0MPa.
The solvent is one of methylene chloride, chloroform, carbon tetrachloride, dichloroethanes.
Nitrosyl h 2 so 4 concentration is to use 1-60% in the catalytic oxidation.
The catalytic oxidation time is 0.5-5 hours.
Advantages of the present invention effect is as follows:
Salt-free nitrosyl sulfuric acid is generated sub- with concentrated nitric acid sulfur dioxide absorption by the redox of nitric acid and sulfur dioxide
Nitryl sulfuric acid can obtain nitrosyl sulfuric acid at concentrations up to 55-60%, and sulfuric acid is less.Salt-free sulfuric acid nitrosyl is for being catalyzed benzene
Methanol oxidation, does not generate sodium bisulfate, does not consume sulfuric acid, also, when supplementing catalyst, nitrosyl sulfuric acid concentration is higher, uses
Amount is less.
Specific embodiment
Embodiment 1
In ptfe autoclave, 2ml methylene chloride is added, 2mmol benzyl alcohol cools to subzero 5 DEG C, quickly stirs
It mixes down, the sulfuric acid nitrosyl that 80mg concentration is 30% is added dropwise, capping kettle enters 0.4MPa oxygen, it reacts 2 hours at room temperature,
Phenmethylol conversion ratio 100%, benzaldehyde selectivity 98%.
Embodiment 2
In ptfe autoclave, 2ml dichloroethanes is added, 2mmol benzyl alcohol cools to subzero 5 DEG C, quickly stirs
It mixes down, the sulfuric acid nitrosyl that 100mg concentration is 12% is added dropwise, capping kettle enters 0.4MPa oxygen, it reacts 2 hours at room temperature,
Phenmethylol conversion ratio 90%, benzaldehyde selectivity 97%.
Embodiment 3
In ptfe autoclave, 2ml methylene chloride is added, 2mmol benzyl alcohol cools to subzero 5 DEG C, quickly stirs
It mixes down, the sulfuric acid nitrosyl that 110mg concentration is 50% is added dropwise, capping kettle enters 0.4MPa oxygen, it reacts 2 hours at room temperature,
Phenmethylol conversion ratio 100%, benzaldehyde selectivity 95%.
Embodiment 4
In ptfe autoclave, 2ml carbon tetrachloride is added, 2mmol benzyl alcohol cools to subzero 5 DEG C, quickly stirs
It mixes down, the sulfuric acid nitrosyl that 200mg concentration is 15% is added dropwise, capping kettle enters 1MPa oxygen, reacts 4 hours at 10 DEG C, benzene
Methanol conversion 100%, benzaldehyde selectivity 99%.
Embodiment 5
Salt-free nitrosyl sulfuric acid catalysis oxidation benzyl alcohol in chloroform solvent prepares benzaldehyde；Salt-free nitrosyl sulfuric acid
Mass ratio with benzyl alcohol is 0.25:1；Catalytic oxidation temperature is 0 DEG C；Oxygen pressure is 0.1MPa；Nitrosyl sulfuric acid
Mass concentration is with 60%；Reaction time is 5 hours.
Embodiment 6
Salt-free nitrosyl sulfuric acid catalysis oxidation benzyl alcohol in chloroform solvent prepares benzaldehyde；Salt-free nitrosyl sulfuric acid
Mass ratio with benzyl alcohol is 1:1；Catalytic oxidation temperature is 50 DEG C；Oxygen pressure is 2.0MPa；Nitrosyl sulfuric acid matter
Measuring concentration is with 1%；Reaction time is 0.5 hour.
Embodiment 7
In ptfe autoclave, 5-20ml methylene chloride is added, 2mmol benzyl alcohol cools to subzero 5 DEG C, fastly
Under speed stirring, the sulfuric acid nitrosyl that 100mg concentration is 20% is added dropwise, capping kettle is passed through 1MPa oxygen, reacts 2 at room temperature
Hour.
Claims (2)
1. application of the salt-free nitrosyl sulfuric acid in the reaction of catalytic phenylmethanol preparing benzaldehyde by oxidizing, it is characterised in that be specially nothing
Catalysis oxidation benzyl alcohol prepares benzaldehyde to salt nitrosyl sulfuric acid in a solvent；The mass ratio of salt-free nitrosyl sulfuric acid and benzyl alcohol is
0.25-1:1；
The catalytic oxidation temperature is 0-50 DEG C；
The oxygen pressure of the catalysis oxidation is 0.1-2.0 MPa；
The solvent is one of methylene chloride, chloroform, carbon tetrachloride, dichloroethanes, and the volume ratio with benzyl alcohol is
5-20:1；
Nitrosyl h 2 so 4 concentration is to use 1-60% in the catalytic oxidation；
The catalytic oxidation time is 0.5-5 hours.
2. salt-free nitrosyl sulfuric acid according to claim 1 answering in the reaction of catalytic phenylmethanol preparing benzaldehyde by oxidizing
With, it is characterised in that the catalytic oxidation temperature is 5-30 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610986937.XA CN106565440B (en) | 2016-11-01 | 2016-11-01 | Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610986937.XA CN106565440B (en) | 2016-11-01 | 2016-11-01 | Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565440A CN106565440A (en) | 2017-04-19 |
| CN106565440B true CN106565440B (en) | 2019-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610986937.XA Expired - Fee Related CN106565440B (en) | 2016-11-01 | 2016-11-01 | Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction |
Country Status (1)
| Country | Link |
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| CN (1) | CN106565440B (en) |
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2016
- 2016-11-01 CN CN201610986937.XA patent/CN106565440B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Acid-assisted catalytic oxidation of benzyl alcohol by NOx with dioxygen;Xuebin Sheng等;《Catalysis Communications》;20100701;第1189–1192页 |
| 无盐亚硝酰硫酸合成工艺研究;谭凤姣;《湘潭师范学院学报(自然科学版)》;20040630;第26卷(第2期);第30-31页 |
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| CN106565440A (en) | 2017-04-19 |
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Granted publication date: 20190705 Termination date: 20191101 |