Summary of the invention
The object of the present invention is to provide a kind of multi-stage oxidizing toluene to prepare the Processes and apparatus of phenyl aldehyde, phenylcarbinol.To realize effectively suppressing the oxidation of primary oxidation product phenyl aldehyde, phenylcarbinol, further improve toluene and the transformation efficiency that replaces toluene; Improve the selectivity of phenyl aldehyde and phenylcarbinol; And can in same set of equipment, realize the continuous production of oxidizing reaction, gas-liquid separation and purifying, step simplifies the operation.
The technology that multi-stage oxidizing toluene prepares phenyl aldehyde, phenylcarbinol may further comprise the steps:
(1) oxidizing reaction: in multi-stage oxidizing reactor drum and Reaction Separation system with gas-liquid separator and band side line separation column or separation column system formation; Use 0.1-50ppm monometallic porphyrin or u oxygen bimetallic porphyrin separately as catalyzer or metalloporphyrin and phthalic imidine (or salt) by weight being 1: the mixed catalyst of 20-100; In temperature of reaction is 80-200 ℃, toluene is stopped 60-180 minute Catalytic Oxygen change into phenyl aldehyde and phenylcarbinol in the multi-stage oxidizing device;
(2) gas-liquid separation and purifying: oxidation mixtures gets into gas-liquid separator; Liquid product ties up to negative pressure or normal pressure or under nitrogen protection, isolates the light constituent of phenyl aldehyde, phenylcarbinol, phenylformic acid and part toluene and water through band side line separation column or separation column, and light constituent toluene after separating water outlet is circulated to oxidizer and continues reaction; The gas phase part is circulated to oxidation reactor with toluene and continues oxidation after condensation separation, noncondensable gas is emptying after treatment.
Described monometallic porphyrin or u-oxygen bimetallic porphyrin have following constructional feature:
The atoms metal M of general formula (I) is transition metal atoms Co or Cu, Ni, Zn, Ru; Atoms metal M in the general formula (II) is Fe or Mn, Cr; The atoms metal M of general formula (III)
1, M
2Be Fe or Mn, Cr; Dentate X in the general formula (II) is acetate or methyl ethyl diketone, halogen, acid radical anion; General formula (I) is (III) middle substituent R (II)
1, R
2, R
3Be hydrogen or alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro.
Metal-salt in metalloporphyrin and the metal-salt mixed catalyst or oxide compound are salt or the oxide compound of transition metal Cu or Zn, Fe, Co, Mn, Cr, Ni.
Equipment of the present invention is by the separation column of multi-stage oxidizing reactor drum and gas-liquid separator and band side entry feed or the Reaction Separation system that separation column system constitutes.
Said multi-stage oxidizing reactor drum is by the individual placed in-line stirred autoclave of the 1-6 of band air-distributor or bubbling reactor or the arbitrary combination between them, on the multi-stage oxidizing reactor drum, is provided with temperature control equipment.
The separation column of said side entry feed or separation column system are for normal pressure or negative pressure and be with nitrogen protection device.
Said separation column is is to be combined with parallelly connected through series, parallel or series connection by a plurality of simple separation columns.
The present invention is the multi-stage oxidizing technology according to the radical circulation coupling mechanism of catalysis of metalloporphyrin hydrocarbon-air oxidation and characteristics proposition; Ability efficient production primary oxidation product phenyl aldehyde, phenylcarbinol in the catalysis of metalloporphyrin atmospheric oxidation toluene system; Adopt multi-stage oxidizing technology can effectively suppress the oxidation of primary oxidation product phenyl aldehyde, phenylcarbinol, the phenyl aldehyde and the phenylcarbinol that utilize system of separation columns in time to extract generation can avoid it that transition oxidation takes place in reactor drum.Compared with present technology the present invention can significantly improve the transformation efficiency of toluene, can reach more than 95% through the experiment toluene conversion, also can improve the selectivity of phenyl aldehyde and phenylcarbinol, and phenyl aldehyde and benzyl alcohol selective reach more than 50%.
Specific embodiments
Below in conjunction with embodiment the present invention is described further, but can not be interpreted as restriction protection domain of the present invention.
Embodiment 1:
Conversion unit comprises that placed in-line successively 6 bands stir and reaction kettle and 2 separation columns of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 5ppm structural formula (III), R down at 190 ℃
1=Cl, R
2=R
3=H; The toluene of M=Fe; The 10atm air is fed the bottom of first stirred autoclave through gas distributor; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed, so analogize.It is 73 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 6th reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes the 3rd stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 50%.
Embodiment 2:
Conversion unit comprises that placed in-line successively 3 bands stir and reaction kettle and 3 separation columns of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 20ppm structural formula (II), R
1=CH
3, R
2=R
3=H; The toluene of M=Cr; The 11atm air is fed the bottom of first stirred autoclave through gas distributor; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed.Control three temperature of reaction kettle and be respectively 190 ℃, 185 ℃, 180 ℃, it is 73 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes first stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 56%.
Embodiment 3:
Conversion unit is stirred by 1 band and reaction kettle and 2 separation columns of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 10ppm structural formula (III), R
1=OCH
3, R
2=R
3=H; The toluene of the N-hydroxyphthalimide of M=Ni and 120ppm; 5atm is contained oxygen 23% gas feeds stirred autoclave through gas distributor bottom; The control temperature of reaction kettle is 90 ℃, and it is 180 minutes that the toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.The reaction mixture that overflows from stirred autoclave gets into separation column system.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes the feeding stirred autoclave and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 97%, phenyl aldehyde benzyl alcohol selective are 60%.
Embodiment 4:
Conversion unit comprises that placed in-line successively 5 bands stir and reaction kettle and 1 separation column of air-distributor constitute.
The technological process of production is: be dissolved with the metalloporphyrin of 40ppm structural formula (II), R 190 ℃ of feedings
1=Cl, R
1=R
2=R
3=H; The toluene of M=Fe; The 9atm air is fed the bottom of first stirred autoclave through gas distributor; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed, so analogize.It is 100 minutes that the toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 5th reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes second stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 96%, phenyl aldehyde benzyl alcohol selective are 55%.
Embodiment 5:
Conversion unit comprises that placed in-line successively 1 bubbling column reactor and 1 stirred autoclave and 3 separation columns constitute.
The technological process of production is: be dissolved with the metalloporphyrin of 15ppm structural formula (I), R 100 ℃ of feedings
1=R
2=R
3=H; The toluene of the N-hydroxyphthalimide of M=Co and 200ppm; The 10atm air is fed the bottom of bubble tower reaction kettle through gas distributor, the bottom of feeding stirred autoclave after the reaction solution that overflows by bubble tower reaction kettle top and the air mixed.It is 150 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.The reaction mixture that overflows from stirred autoclave gets into separation column system.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes first stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 55%.
Embodiment 6:
Conversion unit comprises that placed in-line successively 3 bands stir and reaction kettle and 2 separation columns of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 25ppm structural formula (II), R
1=Cl, R
1=R
2=R
3=H, the Co of M=Mn and 100ppm (OAC)
2Toluene; The 12atm air is fed the bottom of first stirred autoclave through gas distributor; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed.Control three temperature of reaction kettle and be respectively 200 ℃, 160 ℃, 130 ℃, it is 120 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes first stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 51%.
Embodiment 7:
Conversion unit comprises that placed in-line successively 3 bands stir and reaction kettle and 2 separation columns of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 2ppm structural formula (I), R down at 190 ℃
2=OH, R
1=R
3=H; The toluene of M=Cu; 15atm is contained oxygen 17% gas feeds first stirred autoclave through gas distributor bottom; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed.Control three temperature of reaction kettle and be respectively 190 ℃, 175 ℃, 160 ℃, it is 110 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes first stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 52%.
Embodiment 8:
Conversion unit comprises that placed in-line successively 3 bands stir and reaction kettle and 2 band multidraw fractionating towers of air-distributor constitute.
The technological process of production is: feed the metalloporphyrin that is dissolved with 8ppm structural formula (III), R down at 190 ℃
1=NO
2, R
2=H, R
3=Br; The toluene of M=Mn; 8atm is contained oxygen 25% gas feeds first stirred autoclave through gas distributor bottom; Feed the bottom of second stirred autoclave after reaction solution that overflows by first stirred autoclave top and the air mixed, pass through the 3rd stirred autoclave after the reaction solution that overflows from second stirred autoclave top and the air mixed.It is 65 minutes that control toluene flow velocity makes mean residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Get into separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure article of toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid.The toluene that reclaims mixes first stirred autoclave of feeding and carries out secondary oxidation with the toluene that contains the catalysis of metalloporphyrin agent.Said process circulates continuously.Toluene conversion 95%, phenyl aldehyde benzyl alcohol selective are 55%.