CN105801376B - Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol - Google Patents
Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol Download PDFInfo
- Publication number
- CN105801376B CN105801376B CN201610305282.5A CN201610305282A CN105801376B CN 105801376 B CN105801376 B CN 105801376B CN 201610305282 A CN201610305282 A CN 201610305282A CN 105801376 B CN105801376 B CN 105801376B
- Authority
- CN
- China
- Prior art keywords
- benzene
- phenol
- catalyst
- silica gel
- ion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of production method of benzene direct oxidation phenol.It is characterized in that in solvent-free gentle reaction system, using benzene as raw material, 30% hydrogen peroxide is oxidant, and under functional silica gel supported imidazole ion liquid catalytic action, high-purity phenol has been synthesized by high-selectivity oxidation reaction.The reaction system has mild condition, and phenol yield and selectivity are high, simple to operate, while catalyst can be reused with good recovery, no Ecological Environment Risk, be a kind of efficient, environment-friendly production method, be advantageous to industrialized production.
Description
Technical field
The present invention relates to functional silica gel supported imidazole ion liquid catalysis benzene high-selectivity oxidation to prepare the new of phenol
Method, belong to chemical technology field.
Technical background
Phenol is a kind of important industrial chemicals, having many uses industrially, be widely used in various air aldehyde resins,
The synthesis of the compounds such as phenol derivatives, acids, amine.Now, the industrial manufacture process of phenol mainly has cumene method, sulfonation
Method and toluol-benzene formic acid method.Cumene method is industrially to prepare the most widely used method of phenol, base at present in three kinds of methods
This upper more than 90% phenol synthesizes in this way.Different phenylpropyl alcohol method prepares phenol and more defect be present：Synthetic line is grown, always
Yield is relatively low (only 5% or so), and atom utilization is low, raw material serious waste in short supply, and production cost is high；Accessory substance causes ring
The problems such as serious pollution in border；Domestic and international scientists are promoted to make great efforts to explore new synthetic method and route.All the time, benzene
The characteristics of direct oxidation prepares phenol because it has green, and Atom economy is high, by the extensive pass of domestic and international chemist
Note, it is the new focus of phenol preparation technology research and development.Wherein, phenol is prepared by oxidant Direct Catalytic Oxidation benzene of hydrogen peroxide
(Y.Morimoto,S.Bunno,N.Fujieda,H.Sugimoto,S.Itoh,J.Am.Chem.Soc.,2015,137,
5867), accessory substance only in course of reaction is water, has the advantages that route is short, Atom economy is high, therefore be considered as always
Be most be hopeful substitute cumene method a kind of clean preparation method, also always various countries research emphasis.
Ionic liquid refers to what is be made up of organic cation and inorganic or organic anion, there is steam to force down, be non-combustible,
The series of advantages such as heat endurance is high, good thermal conductivity.Ionic liquid can come as the solvent and catalyst of green
Use.Ionic liquid combines the advantages of homogeneous catalyst and heterogeneous catalyst, can as catalyst " carrier " catalysis and
Unique effect is played during organic reaction, is the most reaction medium of prospect and ideal catalytic body in Green Chemistry
System.Patent CN02108941.8 is proposed in 1- octyl group -3- methylimidazole hexafluorophosphate ion liquid systems, dodecyl sulphur
The reaction of the sour lower catalysis hydrogen peroxide oxidation Benzene to phenol of iron salt catalyst effect.Traditional ionic liquid is anti-in benzene oxidatoin phenol
Should aspect have unique catalytic activity (X.Hu, L.Zhu, X.Wang, B.Guo, J.Xu, G.Li, C.Hu,
J.Mol.Catal.A:Chem., 2011,342-343,41), there is also ionic liquid dosage is big, catalyst system and catalyzing and product separation
The shortcomings of purification difficult, so practical application is very limited.In view of conventional ion liquid is in the important of organic catalysis field
The shortcomings of application value and its usage amount are big, recovery is difficult, develop new there is high catalytic activity and can conveniently reclaim and repeat
Use load-type ion liquid catalyst tool be of great significance (J.Yang, L.Zhou, X.Guo, L.Li,
P.Zhang,R.Hong,T.Qiu,Chem.Eng.J.,2015,280,147).For Pyrogentisinic Acid's industrial production, safe and stable,
High-quality, method in high yield, simple to operate and technique are undoubtedly most attractive.
The content of the invention
" green " production method of efficient benzene direct oxidation phenol it is an object of the invention to provide a kind of simple.
The technical solution for realizing the purpose of the present invention is：Functional silica gel supported imidazole ion liquid material is catalyzed
Benzene hydrogen peroxide oxidation prepares the new method of phenol, i.e., using benzene as raw material, 30% hydrogen peroxide is oxidant, silica gel supported ionic liquid
Body is catalyst, and the synthetic reaction of phenol is realized under normal pressure condition of no solvent.
The preparation method of silica gel supported ionic-liquid catalyst used in the present invention referring to document (J.Yang, L.Zhou,
X.Guo,L.Li,P.Zhang,R.Hong,T.Qiu,Chem.Eng.J.,2015,280,147；S.Xun,W.Zhu,D.Zheng,
H.Li,W.Jiang,M.Zhang,Y.Qin,Z.Zhao,H.Li,RSC Adv.,2015,5,43528；W.Zhang,Q.Wang,
H.Wu, P.Wu, M.He, Green Chem., 2014,16,4767), its chemical principle prepared and structure are as follows：
Thermal stability analysis test result indicates that, such silica gel supported ionic-liquid catalyst better heat stability,
Less than 260 DEG C can stablize use.
The mol ratio of material used in the present invention is benzene：30% hydrogen peroxide=1:0.9~2, catalyst amount is the total matter of material
The 5~15% of amount, described material and silica gel supported ionic-liquid catalyst, which proportionally feed intake, mixes reaction.
Reaction temperature of the present invention is 30~60 DEG C.
Reaction time of the present invention is 1~4 hour.
Catalyst of the present invention is silica gel supported tetrafluoroborate ionic liquid, silica gel supported imidazoles hexafluoro
Phosphate ion liquid, silica gel supported imidazoles iron chloride salt ionic liquid, silica gel supported imidazoles copper chloride ionic liquid
In one kind.
A kind of method of silica gel supported imidazole ion liquid catalysis benzene hydrogen peroxide oxidation phenol of the present invention, reaction
After end, cooling and standings, catalyst granules is sunken to drag, and net product benzene is can obtain after the complete benzene of unreacted is recovered by filtration
Phenol, filter cake catalyst can be recyclable reuse without processing, by benzene：30% hydrogen peroxide=1:0.9~2 ratio feed intake into
Row next group catalytic oxidation.
The catalytic oxidation principle of the present invention is as follows：
According to the method provided by the invention for preparing phenol, its key technology be using prepare silica gel supported imidazoles from
Sub- liquid catalyst benzene feedstock and oxidant hydrogen peroxide carry out oxidation reaction and obtain phenol.Compared with prior art, its is excellent by the present invention
Put and be：(1) silica gel supported imidazole ion liquid is used, it is convenient to prepare, and activity is high, and dosage is few, and stability is good, and catalyst does not lose
It is living, it can be recycled.(2) reaction is heterogeneous catalytic oxidation, and phenol product and catalyst separation are simple, and catalyst can facilitate
Recovery is reused.(3) whole reaction system green high-efficient, reaction condition are gentle, and phenol product selectivity is high, and hydrogen peroxide utilizes
Rate is high, and system is not added with other organic solvents, and system is environment-friendly.
Brief description of the drawings
Accompanying drawing is the flow for the method that the present invention is catalyzed benzene direct oxidation phenol with silica gel supported imidazole ion liquid
Figure.
Embodiment
Implementation below is only the description to best mode for carrying out the invention, is not had to the scope of the present invention any
Limitation, it is further explained by means of the following examples the essence of the present invention.
Embodiment 1
In 500mL round-bottomed flasks, benzene (1.1mol), silica gel supported tetrafluoroborate ionic liquid are added
(15g), 30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cooling, filter back
Catalyst is received, filtrate is distilled to recover benzene, obtains phenol product, yield 12.1%.GC-MS analysis results show, phenol selectivity
98.7%.
Embodiment 2
In 500mL round-bottomed flasks, benzene (1.1mol), silica gel supported limidazolium hexafluorophosphate ionic liquid are added
(15g), 30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cooling, filter back
Catalyst is received, filtrate is distilled to recover benzene, obtains phenol product, yield 21.5%.GC-MS analysis results show, phenol selectivity
97.8%.
Embodiment 3
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles iron chloride salt ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 69.5%.GC-MS analysis results show, phenol selectivity 83.6%.
Embodiment 4
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol sterling, yield 58.9%.GC-MS analysis results show that phenol is unique product.
Embodiment 5
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (5g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol sterling, yield 23.2%.GC-MS analysis results show that phenol is unique product.
Embodiment 6
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (10g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol sterling, yield 46.7%.GC-MS analysis results show that phenol is unique product.
Embodiment 7
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (20g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 57.8%.GC-MS analysis results show, phenol selectivity 96.6%.
Embodiment 8
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 30 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 47.2%.GC-MS analysis results show, phenol selectivity 97.5%.
Embodiment 9
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 60 DEG C continue stirring reaction 2.5 hours.Cool down, catalysis is recovered by filtration
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 42.8%.GC-MS analysis results show, phenol selectivity 82.4%.
Embodiment 10
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 1 hour.Cool down, catalyst be recovered by filtration,
Filtrate is distilled to recover benzene, obtains phenol sterling, yield 21.4%.GC-MS analysis results show that phenol is unique product.
Embodiment 11
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2 hours.Cool down, catalyst be recovered by filtration,
Filtrate is distilled to recover benzene, obtains phenol sterling, yield 56.7%.GC-MS analysis results show that phenol is unique product.
Embodiment 12
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 3 hours.Cool down, catalyst be recovered by filtration,
Filtrate is distilled to recover benzene, obtains phenol product, yield 55.6%.GC-MS analysis results show, phenol selectivity 92.2%.
Embodiment 13
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 4 hours.Cool down, catalyst be recovered by filtration,
Filtrate is distilled to recover benzene, obtains phenol product, yield 54.2%.GC-MS analysis results show, phenol selectivity 90.4%.
Embodiment 14
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (1.5mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, be recovered by filtration and urge
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 53.8%.GC-MS analysis results show, phenol selectivity
94.1%.
Embodiment 15
In 500mL round-bottomed flasks, addition benzene (1.1mol), silica gel supported imidazoles copper chloride ionic liquid (15g),
30% hydrogen peroxide (2.2mol) is slowly added under stirring, after at 45 DEG C continue stirring reaction 2.5 hours.Cool down, be recovered by filtration and urge
Agent, filtrate are distilled to recover benzene, obtain phenol product, yield 47.8%.GC-MS analysis results show, phenol selectivity
90.2%.
Embodiment 16
Catalyst in embodiment 4 is reclaimed, catalytic reaction is carried out by each condition in embodiment 4, reuses recovery
Catalyst 4 times, experimental result show that catalyst activity does not subtract, phenol yield 50~59%, phenol selectivity more than 95%.
Embodiment 17
Catalyst in embodiment 3 is reclaimed, catalytic reaction is carried out by each condition in embodiment 3, reuses recovery
Catalyst 6 times, experimental result show that catalyst activity does not subtract, phenol yield 60~68%, phenol selectivity more than 80%.
The present invention has that technique is simple, mild condition, phenol selectivity are high, and the easily separated purifying of product, system are environment-friendly
The advantages of.
Claims (3)
1. a kind of production method of silica gel supported imidazole ion liquid catalysis benzene direct oxidation phenol, it is characterised in that make
With load-type ion liquid heterogeneous catalytic system, using 30% hydrogen peroxide as oxidant, benzene is raw material, is added without other solvents,
Normal pressure, stirring reaction 1~4 hour at 30~60 DEG C, rear cold filtration, isolated phenol product；Described is used as catalyst
Load-type ion liquid there is following structure：
The wherein species anion=BF of anion4、PF6、FeCl4Or CuCl3。
2. according to the method for claim 1, it is characterised in that the mol ratio of material used is benzene：30% hydrogen peroxide=1:
0.9~2, catalyst amount is the 5~15% of material gross mass, and described material, ionic-liquid catalyst proportionally feeds intake
Mix reaction.
3. according to the method for claim 1, it is characterised in that product and catalysis can be achieved by filtering after completion of the reaction
The separation of agent, product phenol and the complete benzene of unreacted are contained in filtrate, be distilled to recover benzene and can obtain phenol product, filter cake is
It is catalyst load-type ion liquid, can be recycled and reused without processing, is fed intake progress according to benzene and hydrogen peroxide mol ratio
Next batch catalytic reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610305282.5A CN105801376B (en) | 2016-05-10 | 2016-05-10 | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610305282.5A CN105801376B (en) | 2016-05-10 | 2016-05-10 | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801376A CN105801376A (en) | 2016-07-27 |
| CN105801376B true CN105801376B (en) | 2018-01-16 |
Family
ID=56456666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610305282.5A Active CN105801376B (en) | 2016-05-10 | 2016-05-10 | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801376B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906484A (en) * | 2016-06-02 | 2016-08-31 | 三峡大学 | Method for preparing phenol by directly oxidizing benzene |
| CN107983408B (en) * | 2017-11-29 | 2021-05-18 | 三峡大学 | Method for preparing sulfoxide catalyst and selectively preparing sulfoxide compound by using sulfoxide catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010207688A (en) * | 2009-03-09 | 2010-09-24 | Univ Of Tokyo | Method for preparing catalyst for manufacturing phenol, catalyst prepared by the preparing method and method for manufacturing phenol |
| CN105521825A (en) * | 2014-09-30 | 2016-04-27 | 中国石油天然气股份有限公司 | Catalyst for preparing phenol by benzene oxidation and preparation method and application thereof |
-
2016
- 2016-05-10 CN CN201610305282.5A patent/CN105801376B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010207688A (en) * | 2009-03-09 | 2010-09-24 | Univ Of Tokyo | Method for preparing catalyst for manufacturing phenol, catalyst prepared by the preparing method and method for manufacturing phenol |
| CN105521825A (en) * | 2014-09-30 | 2016-04-27 | 中国石油天然气股份有限公司 | Catalyst for preparing phenol by benzene oxidation and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Highly selective and green aqueous–ionic liquid biphasic hydroxylation of benzene to phenol with hydrogen peroxide;Jiajian Peng等;《Green Chemistry》;20030320;第5卷;第224-226页 * |
| Hydroxylation of Benzene to Phenol via Hydrogen Peroxide in Hydrophilic Triethylammonium Acetate Ionic Liquid;HU Xiao-ke等;《CHEM. RES. CHINESE UNIVERSITIES》;20111231;第27卷(第3期);第503—507页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801376A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101664700B (en) | Load-type ion liquid catalyst and preparation method and application thereof | |
| CN101485990B (en) | Solid supported heteropoly acid catalyst and preparation method thereof | |
| CN104130216B (en) | The technique of hydrogen peroxide direct oxidation propylene propane mixture continuous preparation of epoxypropane | |
| CN105237336A (en) | Method for synthesizing dimethyl carbonate and ethylene glycol by catalyzing transesterification through load type ion liquid | |
| CN104447443A (en) | Preparation method for apremilast and intermediate of apremilast | |
| CN103265405A (en) | Method for preparing 1,2-cyclohexanediol through carrying out catalytic oxidation on cyclohexene by using phase transfer catalyst | |
| CN105801376B (en) | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol | |
| CN102040584B (en) | Synthesis method of dicyclohexyl-18-crown-6 | |
| CN105906484A (en) | Method for preparing phenol by directly oxidizing benzene | |
| CN107626349A (en) | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid | |
| CN108067304A (en) | A kind of mesoporous function hybrid material and preparation method and application | |
| CN104628991A (en) | Method for synthesizing o-cresol formaldehyde epoxy resin by using cosolvent and recovering cosolvent | |
| CN102643185A (en) | Green and simple preparation method for 2,3,5-trimethylbenzoquinone (TMBQ) | |
| CN102040572B (en) | Production method of benzofuranone | |
| CN102757407B (en) | Allyl chloride epoxidation method for preparing epichlorohydrin | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN103450010B (en) | Method for preparing cyclohexanecarboxylic acid | |
| CN106673952A (en) | Method for catalytic synthesis of benzyl toluene by activated clay-loaded ferric trichloride (FeCl3) solid acid catalyst | |
| CN103012079A (en) | Method for synthesizing ethylene glycol allyl ether under catalysis of solid base catalyst | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN107400046A (en) | Acetone liquid phase one-step method prepares the process of methyl iso-butyl ketone (MIBK) | |
| CN107417541A (en) | The preparation technology of para aminophenyl ethyl ether and aniline | |
| CN102702043A (en) | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase | |
| CN108714436B (en) | Method for recovering activity of heteropoly acid catalyst for synthesizing epoxy chloropropane | |
| CN110724116B (en) | Preparation method and production system of vicinal diol compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211230 Address after: 551199 1-09, No.13 Zhenfu Road, Dongmen neighborhood committee, Yongjing Town, Xifeng County, Guiyang City, Guizhou Province Patentee after: Guiyang Yuguan Technical Service Center Address before: 443002 No. 8, University Road, Yichang, Hubei Patentee before: CHINA THREE GORGES University Patentee before: Huaqiang Chemical Group Co., Ltd |