CN101607867A - Multi-stage oxidizing toluene prepares the Processes and apparatus of phenyl aldehyde, phenylcarbinol - Google Patents
Multi-stage oxidizing toluene prepares the Processes and apparatus of phenyl aldehyde, phenylcarbinol Download PDFInfo
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- CN101607867A CN101607867A CNA2009103051288A CN200910305128A CN101607867A CN 101607867 A CN101607867 A CN 101607867A CN A2009103051288 A CNA2009103051288 A CN A2009103051288A CN 200910305128 A CN200910305128 A CN 200910305128A CN 101607867 A CN101607867 A CN 101607867A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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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
- C07C45/33—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 CHx-moieties
- C07C45/34—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 CHx-moieties in unsaturated compounds
- C07C45/36—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 CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the Processes and apparatus that a kind of toluene atmospheric oxidation prepares phenyl aldehyde, phenylcarbinol.Be in multi-stage oxidizing reactor and Reaction Separation system with gas-liquid separator and band side line separation column or separation column system formation, using 0.1-50ppm monometallic porphyrin or u-oxygen bimetallic porphyrin is 1 as catalyzer or metalloporphyrin and phthalic imidine (or salt) separately by weight: 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; Again through gas-liquid separation and purifying.Compared with the prior art 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%.
Description
Technical field
The present invention relates to the Processes and apparatus that a kind of multi-stage oxidizing toluene prepares phenyl aldehyde, phenylcarbinol.
Background technology
03118066.3 the selectivity catalytic air oxidation toluene that discloses my application becomes the method for aldehyde and alcohol with replacement toluene. be to feed under the 2-10atm air conditions, control reaction temperature is 140-160 ℃, reaction pressure is under the 0.1-1MPa condition, select for use the supported metalloporphyrin that constitutes by physics or chemical process with one or more or above-mentioned metalloporphyrin of the μ-oxygen bimetallic porphyrin of biological enzyme similar and monometallic porphyrin and inorganic and organic polymer separately as catalyzer, catalyst concn is 1-40ppm, and catalytic air oxidation toluene becomes phenyl aldehyde and phenylcarbinol; Replace toluene conversion and change between 10-50%, the yield of substituted benzaldehyde and substituted benzyl alcohol changes between 60-90%.But this reaction is carried out in an oxidation reactor, owing to contain toluene, water, phenyl aldehyde, phenylcarbinol, phenylformic acid and other by product in the liquid reaction mixture, and further oxidation also may take place in primary oxidation product phenyl aldehyde, phenylcarbinol; Cause the purity of product not so good, toluene and replacement toluene conversion are still undesirable; In order to obtain highly purified phenyl aldehyde, phenylcarbinol, must adopt miscellaneous equipment that it is carried out refinement treatment and purification in addition in addition, operation be complicated.
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 the transformation efficiency of toluene and replacement 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 and Reaction Separation system with gas-liquid separator and band side line separation column or separation column system formation, using 0.1-50ppm monometallic porphyrin or u-oxygen bimetallic porphyrin is 1 as catalyzer or metalloporphyrin and phthalic imidine (or salt) separately by weight: 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 enters gas-liquid separator, liquid product ties up to negative pressure or normal pressure or isolate the light constituent of phenyl aldehyde, phenylcarbinol, phenylformic acid and part toluene and water under nitrogen protection 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 M1 of general formula (III), M2 are 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 and gas-liquid separator and band side entry feed or the Reaction Separation system that separation column system constitutes.
Described multi-stage oxidizing reactor 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, is provided with temperature control equipment on the multi-stage oxidizing reactor.
The separation column of described side entry feed or separation column are normal pressure or negative pressure and are with nitrogen protection device.
Described separation column is is to be combined with in parallel by series, parallel or series connection by a plurality of simple separation columns.
The present invention is the multi-stage oxidizing technology according to the free radical circulation coupling mechanism of catalysis of metalloporphyrin hydrocarbon-air oxidation and characteristics proposition, energy 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.Compared with the prior art 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
The invention will be further described below in conjunction with embodiment, but can not be interpreted as limiting the scope of the invention.
Embodiment 1:
Conversion unit comprises that placed in-line successively 6 bands stir and reactor 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, by the 3rd stirred autoclave, so analogize after reaction solution that overflows from second stirred autoclave top and the air mixed.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%.Enter separation column system from the 6th reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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 reactor 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%.Enter separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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 reactor 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 ℃, 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 enters separation column system.After separating, obtain the pure product 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 reactor 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, by the 3rd stirred autoclave, so analogize after reaction solution that overflows from second stirred autoclave top and the air mixed.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%.Enter separation column system from the 5th reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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 reactor through gas distributor, the bottom of feeding stirred autoclave after the reaction solution that overflows by bubble tower reactor 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 enters separation column system.After separating, obtain the pure product 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 reactor 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%.Enter separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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 reactor 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%.Enter separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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 reactor 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%.Enter separation column system from the 3rd reaction mixture that stirred autoclave overflows.After separating, obtain the pure product 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%.
Claims (5)
1. multi-stage oxidizing toluene prepares the technology of phenyl aldehyde, phenylcarbinol, it is characterized in that, may further comprise the steps:
(1) oxidizing reaction: be in multi-stage oxidizing reactor and Reaction Separation system with gas-liquid separator and band side line separation column or separation column system formation, using 0.1-50ppm monometallic porphyrin or u-oxygen bimetallic porphyrin is 1 as catalyzer or metalloporphyrin and phthalic imidine (or salt) separately by weight: 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 enters gas-liquid separator, liquid product ties up to negative pressure or normal pressure or isolate the light constituent of phenyl aldehyde, phenylcarbinol, phenylformic acid and part toluene and water under nitrogen protection 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.
2. the specific equipment of the described technology of claim 1 is characterized in that, by the separation column of multi-stage oxidizing reactor and gas-liquid separator and band side entry feed or the Reaction Separation system that separation column system constitutes.
3. specific equipment according to claim 2, it is characterized in that, described multi-stage oxidizing reactor 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, is provided with temperature control equipment on the multi-stage oxidizing reactor.
4. specific equipment according to claim 2 is characterized in that, the separation column of described side entry feed or separation column are normal pressure or negative pressure and are with nitrogen protection device.
5. specific equipment according to claim 2 is characterized in that, described separation column is is to be combined with in parallel by series, parallel or series connection by a plurality of simple separation columns.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103051288A CN101607867B (en) | 2009-08-03 | 2009-08-03 | Technique for using methylbenzene to prepare benzaldehyde and benzene methanol by multistage oxidation and equipment |
| PCT/CN2009/074678 WO2011015000A1 (en) | 2009-08-03 | 2009-10-29 | Process and device for preparing benzaldehyde and benzyl alcohol by multistage oxidation of toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103051288A CN101607867B (en) | 2009-08-03 | 2009-08-03 | Technique for using methylbenzene to prepare benzaldehyde and benzene methanol by multistage oxidation and equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101607867A true CN101607867A (en) | 2009-12-23 |
| CN101607867B CN101607867B (en) | 2012-05-30 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103051288A Expired - Fee Related CN101607867B (en) | 2009-08-03 | 2009-08-03 | Technique for using methylbenzene to prepare benzaldehyde and benzene methanol by multistage oxidation and equipment |
Country Status (2)
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|---|---|
| CN (1) | CN101607867B (en) |
| WO (1) | WO2011015000A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070382A (en) * | 2011-01-19 | 2011-05-25 | 山东瀛洋香精香料有限公司 | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene |
| CN103130639A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Method for rectification and separation of benzoic acid, benzaldehyde, and toluene by single tower sidestream |
| CN103694093A (en) * | 2013-12-23 | 2014-04-02 | 北京工业大学 | Method for preparing p-methoxybenzaldehyde perfume in presence of metalloporphyrin through catalytic oxidation of p-methoxytoluene |
| CN103755520A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing substituted benzyl alcohol, substituted benzaldehyde and substituted benzyl acid through oxidizing substituted methylbenzene with air based on gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103819480A (en) * | 2014-03-11 | 2014-05-28 | 沅江华龙催化科技有限公司 | Continuous production technology for tetra-aryl-bi-metal porphyrin |
| CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
| CN105237343A (en) * | 2015-09-29 | 2016-01-13 | 衢州群颖化学科技有限公司 | Coproduction method of methyl benzyl alcohol, methyl benzaldehyde, and methyl benzoic acid |
| CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494134C (en) * | 2003-02-08 | 2009-06-03 | 湖南大学 | Process for preparing aldehyde and alcohol by selectively catalytic air oxidation for toluene and substituted toluene |
| CN1215027C (en) * | 2003-09-12 | 2005-08-17 | 湖南大学 | Process for preparing benzaldehyde, phenylcarbinol and benzoic acid |
| CN101362687B (en) * | 2008-10-08 | 2012-04-11 | 湖南大学 | Method and equipment for preparing terephthalic acid by air oxidation of p-xylene |
-
2009
- 2009-08-03 CN CN2009103051288A patent/CN101607867B/en not_active Expired - Fee Related
- 2009-10-29 WO PCT/CN2009/074678 patent/WO2011015000A1/en active Application Filing
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070382A (en) * | 2011-01-19 | 2011-05-25 | 山东瀛洋香精香料有限公司 | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene |
| CN102070382B (en) * | 2011-01-19 | 2014-04-16 | 山东瀛洋香精香料有限公司 | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene |
| CN103130639A (en) * | 2011-11-23 | 2013-06-05 | 中国石油化工股份有限公司 | Method for rectification and separation of benzoic acid, benzaldehyde, and toluene by single tower sidestream |
| CN103694093A (en) * | 2013-12-23 | 2014-04-02 | 北京工业大学 | Method for preparing p-methoxybenzaldehyde perfume in presence of metalloporphyrin through catalytic oxidation of p-methoxytoluene |
| CN103755520A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing substituted benzyl alcohol, substituted benzaldehyde and substituted benzyl acid through oxidizing substituted methylbenzene with air based on gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103819480A (en) * | 2014-03-11 | 2014-05-28 | 沅江华龙催化科技有限公司 | Continuous production technology for tetra-aryl-bi-metal porphyrin |
| CN105237343A (en) * | 2015-09-29 | 2016-01-13 | 衢州群颖化学科技有限公司 | Coproduction method of methyl benzyl alcohol, methyl benzaldehyde, and methyl benzoic acid |
| CN105237343B (en) * | 2015-09-29 | 2017-05-31 | 江西科苑生物药业有限公司 | A kind of method of coproducing methyl phenmethylol, tolyl aldehyde and methyl benzoic acid |
| CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
| CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011015000A1 (en) | 2011-02-10 |
| CN101607867B (en) | 2012-05-30 |
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