CN1296937A

CN1296937A - Process for preparing benzoic acid, henzaldehyde and benzyl alcohol

Info

Publication number: CN1296937A
Application number: CN 00113413
Authority: CN
Inventors: 吴鑫干; 刘惠琴
Original assignee: Hunan University
Current assignee: Hunan University
Priority date: 2000-05-08
Filing date: 2000-05-08
Publication date: 2001-05-30
Anticipated expiration: 2020-05-08
Also published as: CN1113835C

Abstract

A process for preparing benzoic acid, benzaldehyde and benzyl alcohol features the liquid-phase reaction of tolulene with oxygen-contained gas in the presence of Co salt or Co salt plus Mn salt as primary catalyst and bromide as co-catalyst. Its advantages is very high reaction speed.

Description

The preparation of phenylformic acid, phenyl aldehyde, phenylcarbinol

The present invention relates to toluene and in liquid phase, produce the method for phenylformic acid, phenyl aldehyde, phenylcarbinol with oxygen-containing gas oxidation in the presence of catalyzer.

Prior art such as European patent 0036233 etc., in liquid phase, all can only produce phenylformic acid by toluene with oxygen-containing gas oxidation in the presence of cobalt, Mn catalyst, and can not produce simultaneously the by product of economic worth phenyl aldehyde and phenylcarbinol are arranged more, the catalyzer that uses only limits to cobalt salt or manganese salt, the cylindrical empty barrel reactor or the still formula band stirred reactor speed of response that adopt are fast inadequately, and efficient is also undesirable.

The object of the present invention is to provide that a kind of speed of response is faster, efficient is higher, can prepare the method for phenylformic acid, phenyl aldehyde, phenylcarbinol simultaneously.

The present invention includes the monoalkylated benzenes compound in liquid phase with oxygen-containing gas in the presence of Primary Catalysts 10～1000ppm cobalt salt or cobalt salt manganese addition salt, 130～200 ℃ of temperature, under pressure 0.3～0.8MPa condition, stop and carried out oxidation in 1～8 hour, it is characterized in that the bromide of being furnished with Primary Catalysts mol ratio 0.5～3.5 in Primary Catalysts makes promotor, also add other metal-salts of 1/10～1/100 of being furnished with the Primary Catalysts mol ratio and make co-catalyst, and the phenyl aldehyde that adds benzene compound volume 1/100～1/1000 when the reaction beginning is made initiator.Oxygen-containing gas is repeatedly to disperse and react with raw material by the aperture on the turriform sieve plate.

Described cobalt salt or cobalt salt manganese addition salt are preferably the organic acid salt that can be dissolved in reaction mixture, and as benzoate, naphthenate, fragrant hydrochlorate etc., preferably cobalt salt adds the manganese salt of cobalt salt weight 1/10～1/100.Described bromide can be NH ₄Br, NaBr, KBr etc., other metal-salts can be magnesium salts, mantoquita, zinc salt, aluminium salt, antimonic salt, pink salt, nickel salt, molysite, chromic salts, vanadic salts, zirconates etc.

The interpolation bromide is made promotor and is added other metal-salts and make co-catalyst, can reduce the consumption of Primary Catalysts on the one hand, reduce cost, the more important thing is and to improve speed of response greatly, improve reaction efficiency, general speed of response can improve 10 times to 30 times.

Repeatedly disperse by the aperture on the turriform sieve plate and react by means of oxygen-containing gas with raw material, oxygen can high-level efficiency absorb, so efficient improves greatly, the residual oxygen of reactor outlet tail gas reduces greatly, the residual oxygen of outlet tail gas reaches below 0.1%, can also significantly reduce back-mixing, makes bottom product enrichment, and form certain gradient, so do not need to stir.By side line outlet and bottoms outlet collection and separate, can produce phenylformic acid, phenyl aldehyde, phenylcarbinol simultaneously, and other data of productivity ratio improve greatly.The phenylformic acid productive rate is more than 60%, and phenyl aldehyde is more than 20%, and phenylcarbinol is more than 10%, thereby economic benefit greatly improves.

Illustrated below in conjunction with drawings and Examples.

Accompanying drawing is a process flow sheet of the present invention.

By reference to the accompanying drawings: (2) enter reactor (1) from top to bottom through the feed(raw material)inlet for raw material and catalyst, Oxygen-containing gas from air jet pipe (3) from bottom to top and oxidation reaction takes place, reaction give vent to anger through the gas outlet (4) Introduce condenser (5), fixed gas by line (6) again by arranging behind the charcoal absorption meet the requirement of environmental protection Go out. Condensate imports separator (8) by line (7), is separated into organic layer and water layer, and water layer passes through Line (9) is discharged, and organic layer is by line (10) Returning reactor (1), and liquid reaction mixture passes through Line (11) flows to destilling tower (12) from reactor (1), boils being lower than benzaldehyde at this all components The lower boiling of point. Remove by line (14), it mainly is toluene Returning reactor (1) that top products forms, Bottom product flows out by line (13) and enters destilling tower (15), and benzaldehyde, phenmethylol heat up in a steamer in this tower Divide (17) from the higher boiling product, to distill away, enter another destilling tower and further be separated into the benzene first Aldehyde (19), phenmethylol (20), the higher boiling product at the bottom of destilling tower (15) tower is benzoic acid cut (16), Output is reduced pressure again, and distillation manufacture level benzoic acid (22) and other are high boiling substance (23) more, Last residue is tar (24).

Embodiment 1:

Raw material toluene 100kg, Primary Catalysts cobaltous benzoate 80g adds manganese benzoate 8g, adds promotor.NH ₄Br32g, co-catalyst phenylformic acid zirconium 1g with the dilution of 100g water, adds initiator phenyl aldehyde 500g, more than enter reactor from top to bottom by feed(raw material)inlet (2), contain the oxygen air and disperse from bottom to top from the aperture of gas ejector pipe (3) on the turriform sieve plate, 130～150 ℃ of temperature, pressure 0.5～0.7MPa catalyzed oxidation 7 hours, press the final product that gets of above flow process: phenylformic acid 60kg, phenyl aldehyde 20kg, phenylcarbinol 10kg, toluene and heavy constituent 15kg.

Embodiment 2:

Raw material toluene 100kg, cause phenyl aldehyde 500g, Primary Catalysts cobalt naphthenate 60g adds manganese naphthenate 6g, promotor NaBr25g, water 80g dilution is 180～200 ℃ of temperature, pressure 0.5～0.8MPa, catalyzed oxidation 4 hours is pressed the final product that gets of above flow process: phenylformic acid 65kg, phenyl aldehyde 20kg, phenylcarbinol 10kg, toluene and heavy constituent 10kg.

Claims

1, phenylformic acid, phenyl aldehyde, the preparation of phenylcarbinol, comprise toluene in liquid phase with oxygen-containing gas in the presence of Primary Catalysts 10～1000ppm cobalt salt or cobalt salt manganese addition salt, 130～200 ℃ of temperature, under pressure 0.3～0.8MPa condition, stop and carried out oxidation in 1～8 hour, it is characterized in that the bromide of being furnished with Primary Catalysts mol ratio 0.5～3.5 in the Primary Catalysts makes promotor, also add other metal-salts of being furnished with Primary Catalysts mol ratio 1/10～1/100 and make co-catalyst, the phenyl aldehyde that also is added with volume of toluene 1/100～1/1000 is made initiator, and oxygen-containing gas is repeatedly to disperse and react with raw material by the aperture on the turriform sieve plate.