CN1850756A - Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane - Google Patents
Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane Download PDFInfo
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- CN1850756A CN1850756A CNA200610031689XA CN200610031689A CN1850756A CN 1850756 A CN1850756 A CN 1850756A CN A200610031689X A CNA200610031689X A CN A200610031689XA CN 200610031689 A CN200610031689 A CN 200610031689A CN 1850756 A CN1850756 A CN 1850756A
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- reactor
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- cyclohexane
- pimelinketone
- bubbling column
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
This invention discloses cyclohexane air dioxide prepare cyclohexanol, cyclohexanone and adipic acid technique and equipment. Its technique is that in series connecting reaction system in a 4-8 grade kettle reactor that contains agitator, or series connecting reaction system in a 3-7 bubbling column reactor that contains outer cycle, or series connecting reaction system in 2-6 different type reactor, cyclohexane that added catalyst of 1-100PPM metalloporphyrin and 0.1-2.0 PPM air, or oxygen or oxygen enriched air or oxygen denubed air is let in. temperature is 120-160 degree centigrade, reaction for 45-120 minutes. Corresponding equipment is also included in this invention. This invention can restrain train side reaction and reduce generating of depthoxide, so cyclohexane conversion, reaction selectivity and oxidation products yield can be improved.
Description
Technical field
The present invention relates to the Processes and apparatus of a kind of cyclohexane air dioxide prepare cyclohexanol, pimelinketone and hexanodioic acid, especially relating to a kind of is the Processes and apparatus of cyclohexane air dioxide prepare cyclohexanol, pimelinketone and the hexanodioic acid of catalyzer with the metalloporphyrin.
Background technology
Air oxidation of cyclohexane is the important method of preparation pimelinketone.At present, be the non-catalyst oxidation method of Dutch Si Damika our company invention in industrial method of producing pimelinketone by cyclohexane oxidation, its reaction is to carry out under high-temperature and high-pressure conditions, and reaction yield is lower, and selectivity of product is relatively poor.Cyclohexane oxidation is produced the method for pimelinketone under catalysis of metalloporphyrin, and reaction yield and selectivity of product all obviously are better than present non-catalyst oxidation method.For example, WO 98/04538 discloses a kind of method of using monometallic porphyrin gas-liquid catalytic air oxidation alkane and naphthenic hydrocarbon, CN 00113225.3 discloses a kind of method of using monometallic porphyrin/metal-salt compound system and μ-oxygen bimetallic porphyrin difference gas-liquid catalytic air oxidation alkane and naphthenic hydrocarbon, and CN 02139709 discloses a kind of method of using metalloporphyrin gas-liquid catalytic air oxidation hexanaphthene.Because the catalysis of metalloporphyrin air oxidation of cyclohexane has different reaction mechanisms and response feature with no catalysis method oxidizing ethyle alkyl, how to realize that metalloporphyrin gas-liquid catalytic air oxidation hexamethylene hydrocarbon is a problem anxious to be solved at present both at home and abroad.CN 02113940.7 discloses a kind of method of using cobalt dual-metal porphyrin catalytic air oxidation hexanaphthene in laminar flow formula reactor, CN 200310110458.4 discloses a kind of tetraphenylporphyrin iron and tetraphenylporphyrin cobalt respectively at three stills series connection stirred reactor, bubbling style list still reactor, the shell and tube single reactor, the method of catalytic air oxidation hexanaphthene in the laminar flow formula single reactor, these methods can reduce temperature of reaction and pressure, but the reaction later stage still exists the disadvantageous air-teturning mixed phenomenon of oxidizing hydrocarbon, the catalytic effect of metalloporphyrin is still undesirable, cyclohexane conversion, reaction preference and oxidation products yield are still lower.
Summary of the invention
The object of the present invention is to provide the Processes and apparatus of higher catalysis of metalloporphyrin cyclohexane air dioxide prepare cyclohexanol, pimelinketone and hexanodioic acid of a kind of cyclohexane conversion, reaction preference and oxidation products yield.
The technical scheme of the present invention's technology is as follows: in the reactive system of the bubbling column reactor cascade reaction system of the tank reactor cascade reaction system of a 4-8 level belt stirrer or the outer circulation of 3-7 band or 2-6 dissimilar reactors in series, feeding is dissolved with hexanaphthene that the 1-100PPM metalloporphyrin is a catalyzer and air or oxygen or oxygen-rich air or the oxygen-denuded air of 0.1-2.0PPM, under temperature 120-160 ℃ condition, reacted 45-120 minute, molecular oxygen becomes corresponding hexalin, pimelinketone and hexanodioic acid with cyclohexane oxidation.The structural formula of catalyst metal porphyrin is as follows:
Atoms metal M in the structural formula (I) can be transition metal atoms: Fe, Mn, and Cr, Co, Cu, Zn, Ni, Ru etc., dentate X can be acetate, methyl ethyl diketone, halogen and other acid radical anions; Atoms metal M in the structural formula (II)
1, M
2Be atoms such as Fe, Mn, Cr.Substituent R in structural formula (I) and the structural formula (II)
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro.
The present invention's equipment comprises: system that is made of the tank reactor series connection of 4-8 (preferred 5-6) belt stirrer or the system that is made of the bubbling column reactor of 3-7 band outer circulation or the system of being connected the system that constitutes with tubular reactor or being connected the system that constitutes with tubular reactor or connected and constituted by 1-2 the bubbling column reactor of being with outer circulation and the tank reactor of 1-4 belt stirrer by 1-2 the bubbling column reactor of being with outer circulation by the tank reactor of 1-2 belt stirrer, they are connected successively by pipeline.
The present invention's technology is the reaction of high order technology according to the free radical circulation coupling mechanism of catalysis of metalloporphyrin hydrocarbon-air oxidation and characteristics proposition, select for use pressure to improve the reactor of the mass transfer efficiency of material in the reaction system early stage in reaction, accelerated reaction, and adopt the reactor of effectively controlling material back-mixing in the reaction system in the reaction later stage, suppress the consecutive side reaction, reduce the generation of deep oxidation product.The present invention has the effect that improves hexanaphthene reaction conversion ratio, selectivity of product and oxidation products yield.Cyclohexane conversion is between 15-25%, and hexalin, pimelinketone and hexanodioic acid selectivity are greater than 90%.
Embodiment
The invention will be further described below in conjunction with embodiment, but shall not be construed as limiting the scope of the invention.
Embodiment 1
Conversion unit comprises the bubbling column reactor and the tubular reactor of placed in-line successively two bands outer circulation.The technological process of production: feed the metalloporphyrin that is dissolved with 10PPM structural formula (I), R down at 150 ℃
1=H, R
2=R
3=CH
3The hexanaphthene of M=Mn, 0.4MPa is fed the bottom of the 1st bubbling column reactor through the air of gas distributor, reaction solution is gone into the bottom of the 2nd bubbling column reactor by the 1st bubbling column reactor top overflow, contain the hexanaphthene of catalyzer and enter tubular reactor from the 2nd reaction solution that bubbling column reactor top overflows after venturi mixer and air mixed, it is 90 minutes that gate ring hexane flow velocity makes the residence time.The oxidation liquid that comes out from tubular reactor gets adipic acid crystals through refrigerated separation, and filtrate is decomposed after flash distillation, by obtaining hexalin and pimelinketone and hexanodioic acid behind the distillation tower recovery hexanaphthene.Cyclohexane conversion is 15%, hexalin, pimelinketone and hexanodioic acid selectivity 93%.
Embodiment 2
Conversion unit comprises the tank reactor of placed in-line successively 6 belt stirrers.The technological process of production: catalyzer is for having the metalloporphyrin of structural formula (II), R
1=R
2=OCH
3, R
3=Cl, M
1=M
2=Fe, oxygenant is the 0.8MPa air.To contain the hexanaphthene of 2PPM catalyzer and feed the bottom of the 1st reactor through the air of gas distributor, reaction solution is gone into the bottom of the 2nd reactor by the 1st reactor top overflow, temperature of reaction is 145 ℃, reaction pressure is 0.9MPa, enter the 3rd reactor from the 2nd reaction solution that reactor top overflows, then successively by the 4th, 5,6 reactor.It is 45 minutes that gate ring hexane flow velocity makes the residence time, and the control air flow velocity makes the tail oxygen level be no more than 5%.Oxidation liquid decomposes after flash distillation, by obtaining hexalin and pimelinketone and hexanodioic acid behind the distillation tower recovery hexanaphthene.Cyclohexane conversion is 20%, hexalin, pimelinketone and hexanodioic acid selectivity 90%.
Embodiment 3
Conversion unit comprises the tank reactor and the tubular reactor of placed in-line successively 2 belt stirrers.The technological process of production: catalyzer is for having the metalloporphyrin of structural formula (I), R
1=R
2=C
2H
5, R
3=Br, M=Fe, oxygenant is the air that 0.6MPa contains oxygen 25%.The hexanaphthene that will contain the 20PPM catalyzer feeds the bottom of the 1st tank reactor through the air of gas distributor, and reaction solution is gone into the bottom of the 2nd tank reactor by the 1st tank reactor top overflow, and temperature of reaction is 160 ℃.The reaction solution that overflows from the 2nd tank reactor top enters tubular reactor after venturi mixer and air mixed, it is 90 minutes that control toluene flow velocity makes the residence time.The oxidation liquid that comes out from tubular reactor gets the phenylformic acid crystal through refrigerated separation, and filtrate is decomposed after flash distillation, by obtaining hexalin and pimelinketone and hexanodioic acid behind the distillation tower recovery toluene.Cyclohexane conversion is 19%, hexalin, pimelinketone and hexanodioic acid selectivity 90%.
Embodiment 4
Conversion unit comprises the tank reactor of placed in-line successively 2 bubbling column reactors and 3 belt stirrers.The technological process of production: catalyzer is for having the metalloporphyrin of structural formula (II), R
1=R
2=CH
3, R
3=OH, M
1=M
2=Mn, oxygenant is the air that 1MPa contains oxygen 18%, to contain the hexanaphthene of 5PPM catalyzer and feed the bottom of the 1st bubbling column reactor through the air of gas distributor, reaction solution is gone into the bottom of the 2nd bubbling column reactor by the 1st bubbling column reactor top overflow, and temperature of reaction is 120 ℃; Enter the 1st tank reactor from the 2nd reaction solution that bubbling column reactor top overflows, successively by the 2nd, 3 tank reactor, it is 120 minutes that gate ring hexene flow velocity makes the residence time then.Oxidation liquid is through separating, and hexanaphthene recycles, and oxidation products is hexalin and pimelinketone and hexanodioic acid.Cyclohexane conversion is 21%, hexalin, pimelinketone and hexanodioic acid selectivity 91%.
Embodiment 5
Conversion unit comprises placed in-line successively 6 bubbling column reactors.The technological process of production: catalyzer is the metalloporphyrin of structural formula (I), R
1=R
2=Cl, R
3=OH, M=Co, oxygenant is the air that 0.6MPa contains oxygen 26%.To contain the hexanaphthene of 30PPM metalloporphyrin and feed the bottom of the 1st bubbling column reactor through the air of gas distributor, temperature of reaction is 90 ℃.By the bottom that enters the 2nd bubbling column reactor after the 1st reaction solution that bubbling column reactor top overflows and the air mixed, enter the bottom of the 3rd bubbling column reactor after the 2nd reaction solution that bubbling column reactor top overflows and the air mixed, successively by the 4th, 5,6 bubbling column reactor, it is 150 minutes that gate ring hexane flow velocity makes the residence time then.The oxidation liquid that comes out from the 6th bubbling column reactor obtains reaction product hexalin and pimelinketone and hexanodioic acid after reclaiming hexanaphthene through flash distillation and by distillation tower.Cyclohexane conversion is 18%, hexalin, pimelinketone and hexanodioic acid selectivity 91%.
Embodiment 6
Conversion unit comprises that branch connects for two groups successively, again with the tank reactor of 8 belt stirrers of two groups of parallel connections.The technological process of production: catalyzer is for having the metalloporphyrin of structural formula (I), R
1=OC
2H
5, R
2=R
3=H,, M=Cu.Oxygenant is the air of 0.8MPa.To contain the hexanaphthene of 1PPM catalyzer and feed the bottom of every group of the 1st reactor respectively through the air of gas distributor, reaction solution is gone into the bottom of every group of the 2nd reactor by every group of the 1st reactor top overflow, and temperature of reaction is 145 ℃.Enter every group of the 3rd, 4 reactor more successively from every group of the 2nd reaction solution that reactor top overflows.It is 50 minutes that gate ring hexane flow velocity makes the residence time.After the oxidation liquid that comes out from the 4th reactor reclaims hexanaphthene through flash distillation and by distillation tower, reaction product through hydrolysis separate hexalin and pimelinketone.Cyclohexane conversion is 17%, hexalin, pimelinketone and hexanodioic acid selectivity 92%.
Embodiment 7
Conversion unit comprises the tank reactor of placed in-line successively 4 belt stirrers.The technological process of production: catalyzer is for having the metalloporphyrin R of structural formula (II)
1=R
2=C
3H
7, R
3=NO
2, M
1=M
2=Cr, oxygenant is the air that 0.9MPa contains oxygen 30%.The hexanaphthene of 80PPM catalyzer be will contain and bottom with the 1st tank reactor, 160 ℃ of temperature of reaction fed through the air of gas distributor.By the bottom that enters the 2nd reactor after the 1st reaction solution that reactor top overflows and the air mixed, enter the bottom of the 3rd bubbling column reactor after the 2nd reaction solution that reactor top overflows and the air mixed, enter the bottom of the 4th bubbling column reactor after the 3rd reaction solution that reactor top overflows and the air mixed, it is 65 minutes that gate ring hexane flow velocity makes the residence time.The oxidation liquid that comes out from the 4th reactor obtains reaction product hexalin and pimelinketone and hexanodioic acid after reclaiming hexanaphthene through flash distillation and by distillation tower.Cyclohexane conversion is 22%, hexalin, pimelinketone and hexanodioic acid selectivity 90%.
Embodiment 8:
Conversion unit comprises 1 bubbling column reactor and placed in-line with it tubular reactor.The technological process of production: catalyzer is for having the metalloporphyrin and the Cu of structural formula (I)
2Cl
2, R
1=NH
2, R
2=R
3=CH
3, M=Ni, oxygenant is the 1.2MPa air.To contain the hexanaphthene of 40PPM catalyzer and feed the bottom of bubbling column reactor through the air of gas distributor, temperature of reaction is 145 ℃.The reaction solution that overflows from bubbling column reactor top and through the air admission tubular reactor of gas distributor, it is 80 minutes that gate ring hexane flow velocity makes the residence time.The oxidation liquid that comes out from tubular reactor reclaims hexanaphthene by distillation tower after flash distillation, obtain reaction product hexalin and pimelinketone and hexanodioic acid.Cyclohexane conversion is 25%, hexalin, pimelinketone and hexanodioic acid selectivity 91%.
Embodiment 9
Conversion unit comprises placed in-line successively 4 bubbling column reactors.The technological process of production: catalyzer is the metalloporphyrin of structural formula (I), R
1=R
2=OH, R
3=N (NH
3)
2, M=Ru, oxygenant is the 1.6MPa air.To contain the hexanaphthene of 6PPM metalloporphyrin and feed the bottom of the 1st bubbling column reactor through the air of gas distributor, temperature of reaction is 165 ℃; By the bottom of going into the 2nd bubbling column reactor after the 1st reaction solution that bubbling column reactor top overflows and the air mixed, pass through the 3rd, 4 bubbling column reactor more successively after the 2nd reaction solution that bubbling column reactor top overflows and air mixed, it is 85 minutes that gate ring hexane flow velocity makes the residence time.The oxidation liquid that comes out from the 4th bubbling column reactor obtains hexalin and pimelinketone and hexanodioic acid after reclaiming hexanaphthene through flash distillation and by distillation tower.Cyclohexane conversion is 16%, hexalin, pimelinketone and hexanodioic acid selectivity 3%.
Embodiment 10
Conversion unit comprises the tank reactor of placed in-line successively 5 belt stirrers.The technological process of production: adopt the catalysis of metalloporphyrin agent of structural formula (I), R
1=R
2=H, R
3=C
4H
9, M=Pt, oxygenant is the 1.8MPa air.To contain the hexanaphthene of 60PPM catalyzer and feed bottom with the 1st tank reactor through the air of gas distributor, temperature of reaction is 140 ℃.By the bottom that enters the 2nd reactor after the 1st reaction solution that reactor top overflows and the air mixed, behind the reaction solution and air mixed that reaction solution is flowed out by the 2nd reactor top, successively by the 3rd, 4,5 reactor, the temperature of reaction of 3-5 reactor is 190 ℃ again.It is 95 minutes that gate ring hexane flow velocity makes the residence time.The oxidation liquid that comes out from the 5th reactor reclaims hexanaphthene by distillation tower after flash distillation, obtain oxidation products hexalin and pimelinketone and hexanodioic acid.Cyclohexane conversion is 23%, hexalin, pimelinketone and hexanodioic acid selectivity 92%.
Claims (4)
1, a kind of cyclohexane air dioxide prepare cyclohexanol, the technology of pimelinketone and hexanodioic acid, it is characterized in that, in the reactive system of the bubbling column reactor cascade reaction system of the tank reactor cascade reaction system of a 4-8 level belt stirrer or the outer circulation of 3-7 band or 2-6 dissimilar reactors in series, feeding is dissolved with hexanaphthene that the 1-100PPM metalloporphyrin is a catalyzer and air or oxygen or oxygen-rich air or the oxygen-denuded air of 0.1-2.0PPM, under temperature 120-160 ℃ condition, reacted 45-120 minute, molecular oxygen becomes corresponding hexalin with cyclohexane oxidation, pimelinketone and hexanodioic acid.
2, according to the technology of the described cyclohexane air dioxide prepare cyclohexanol of claim 1, pimelinketone and hexanodioic acid, described metalloporphyrin has general formula (I) or structure (II).
General formula (I)
General formula (II)
Atoms metal M in the structural formula (I) can be transition metal atoms: Fe, Mn, and Cr, Co, Cu, Zn, Ni, Ru, dentate X can be acetate, methyl ethyl diketone, halogen and acid radical anion; Atoms metal M in the structural formula (II)
1, M
2Be Fe, Mn, Cr; Structural formula (I) and (II) in substituent R
1, R
2, R
3Hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, nitro.
3, according to claim 1 or 2 described cyclohexane air dioxide prepare cyclohexanol, the equipment of pimelinketone and hexanodioic acid, it is characterized in that, system that comprises the system that is made of the series connection of the tank reactor of 4-8 belt stirrer or be made of the bubbling column reactor of 3-7 band outer circulation or the system of being connected the system that constitutes with tubular reactor or being connected the system that constitutes with tubular reactor or connected and constituted by 1-2 the bubbling column reactor of being with outer circulation and the tank reactor of 1-4 belt stirrer by 1-2 the bubbling column reactor of being with outer circulation by the tank reactor of 1-2 belt stirrer, they are connected successively by pipeline.
According to the equipment of the described cyclohexane air dioxide prepare cyclohexanol of claim 3, pimelinketone and hexanodioic acid, it is characterized in that 4, the tank reactor series system of described belt stirrer is made of the tank reactor series connection of 5-6 belt stirrer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610031689XA CN100393680C (en) | 2006-05-22 | 2006-05-22 | Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane |
| PCT/CN2007/001336 WO2007134521A1 (en) | 2006-05-22 | 2007-04-23 | Apparatus and technology for preparing cyclohexanol, cyclohexanone and adipic acid by air oxidization of cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610031689XA CN100393680C (en) | 2006-05-22 | 2006-05-22 | Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1850756A true CN1850756A (en) | 2006-10-25 |
| CN100393680C CN100393680C (en) | 2008-06-11 |
Family
ID=37132258
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610031689XA Expired - Fee Related CN100393680C (en) | 2006-05-22 | 2006-05-22 | Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100393680C (en) |
| WO (1) | WO2007134521A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010020080A1 (en) * | 2008-08-18 | 2010-02-25 | Guo Cancheng | Process and apparatus for preparing adipic acid by catalytic air oxidation of cyclohexane |
| CN101225067B (en) * | 2007-01-19 | 2011-12-07 | 湖南大学 | Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane |
| CN103755544A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing KA oil and adipic acid through oxidizing cyclohexane with air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103755521A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing KA oil through oxidizing cyclohexane by using air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN107778132A (en) * | 2016-08-25 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method that cyclohexanol and cyclohexanone are prepared based on multilayer guide shell bubbling reactor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191218C (en) * | 2002-10-29 | 2005-03-02 | 湖南大学 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN1247501C (en) * | 2003-01-24 | 2006-03-29 | 中国石油化工股份有限公司 | Catalyst oxdie cyclohexane process |
| CN100402477C (en) * | 2003-03-14 | 2008-07-16 | 湖南大学 | Method for catalytic conversion of alkyl cyclohexanol and alkyl cyclohexanone from air oxidized alkyl cyclohexane |
-
2006
- 2006-05-22 CN CNB200610031689XA patent/CN100393680C/en not_active Expired - Fee Related
-
2007
- 2007-04-23 WO PCT/CN2007/001336 patent/WO2007134521A1/en active Application Filing
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225067B (en) * | 2007-01-19 | 2011-12-07 | 湖南大学 | Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane |
| WO2010020080A1 (en) * | 2008-08-18 | 2010-02-25 | Guo Cancheng | Process and apparatus for preparing adipic acid by catalytic air oxidation of cyclohexane |
| CN103755544A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing KA oil and adipic acid through oxidizing cyclohexane with air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103755521A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing KA oil through oxidizing cyclohexane by using air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103755521B (en) * | 2014-01-26 | 2015-02-18 | 沅江华龙催化科技有限公司 | Method for producing KA oil through oxidizing cyclohexane by using air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN103755544B (en) * | 2014-01-26 | 2015-07-15 | 沅江华龙催化科技有限公司 | Method for producing KA oil and adipic acid through oxidizing cyclohexane with air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor |
| CN107778132A (en) * | 2016-08-25 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method that cyclohexanol and cyclohexanone are prepared based on multilayer guide shell bubbling reactor |
| CN107778132B (en) * | 2016-08-25 | 2021-02-05 | 中国石油化工股份有限公司 | Method for preparing cyclohexanol and cyclohexanone based on multilayer guide cylinder bubble reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007134521A1 (en) | 2007-11-29 |
| CN100393680C (en) | 2008-06-11 |
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