CN106146276B - A kind of method of phenol compound catalysis oxidation synthesis benzoquinone compound - Google Patents
A kind of method of phenol compound catalysis oxidation synthesis benzoquinone compound Download PDFInfo
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- CN106146276B CN106146276B CN201510154630.9A CN201510154630A CN106146276B CN 106146276 B CN106146276 B CN 106146276B CN 201510154630 A CN201510154630 A CN 201510154630A CN 106146276 B CN106146276 B CN 106146276B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
Abstract
The invention discloses a kind of methods of phenol compound catalysis oxidation synthesis benzoquinone compound, belong to the synthesis technical field of benzoquinone compound.Reactant phenol compound, solvent, solid catalyst (onion carbon etc.) oxidant tert-butyl hydroperoxide are added in reactor by this method, and ultrasonic treatment forms suspension, and suspension is heated to 70~100 DEG C, reacts 2~16h；Then reaction mixture is separated, obtains solid catalyst and the liquid mixture containing benzoquinone compound；Liquid mixture separating-purifying obtains product benzoquinone compound.Operation of the present invention process is simple, and non-metallic catalyst used is corrosion-free, cheap, environmentally protective, may be reused；Methylphenol high conversion rate, target product methyl-p-benzoquinone are selectively good.
Description
Technical field
The present invention relates to the synthesis technical fields of benzoquinone compound, and in particular to a kind of phenol compound catalysis oxidation
The method for synthesizing benzoquinone compound.
Background technique
Benzoquinone compound is not only widely used in medical treatment, chemical industry, bio-pharmaceutical etc., while being also a kind of important to have
Machine intermediate.For example, common 2,3,6- trimethyl 1,4-benzoquinone are the main intermediates of vitamin E.Such 1,4-benzoquinone is in foreign countries
Have production, and domestic 2,3,6- required trimethyl 1,4-benzoquinone rely primarily on import.- 1,4 1,4-benzoquinone of 2,6- dimethyl is one
The antioxidant of kind high activity, has the medicine curative effects such as anti-aging.Report is reacted in the catalysis of 1,4-benzoquinone class at present, common mainly to relate to
And two methods: one is the direct oxidation methods of phenol.The U.S. Patent application of Publication No. US4360469 provides one kind
With the salicil amine ethyl cobalt method that the oxidation of catalysis of phenol class prepares 1,4-benzoquinone class under the assistance of molecular oxygen.This method yield
Height, but catalyst preparation process is complicated, it is expensive, and high poison, be not suitable for industrial application.Beller et al.
(Chem.Eur.J.2010,16,10300) it proposes to utilize ferric chloride hexahydrate Oxybenzene under the action of organic amine and hydrogen peroxide
The method that phenols prepares 1,4-benzoquinone class.But this method belongs to homogeneous catalysis, and there are 1,4-benzoquinone class is selectively lower, catalyst is not easy
The disadvantages of recycling.Another method is the direct oxidation method of arene.Beller et al.
(Adv.Synth.Catal.2010,352,1615-1620) it develops again using ruthenium base complex as catalyst oxidizing aromatic hydrocarbons class
The method for preparing 1,4-benzoquinone class.This method is equally faced with the problems such as selectivity is low.In short, at present used in both methods
Catalyst be directed to metal catalyst, such as molecular sieve, miscellaneous more modified complexs and noble metal.The catalyst has
Synthetic method is complicated, structure easily occurs to collapse and atrophy, catalyst life are short, required chemical environment harshness, or even needs strong acid
The disadvantages of highly basic.
In view of deficiency existing for above-mentioned all kinds of catalyst, develop it is a kind of it is cheap, be easily isolated and there is good low temperature
The solid catalyst that active recyclable stabilization utilizes is the emphasis of phenol oxidation research.
In recent years, simple, cheap, environmental-friendly, chemical property is stable and there is catalysis to live due to preparing for carbon material
Property, by wide coverage.And up to the present, do not have also using carbon materials such as onion carbon as heterogeneous catalysis, selective catalysis oxygen
Change the open report that phenol compound prepares corresponding benzoquinone compound technique.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing preparation methyl-p-benzoquinone class technique, a kind of phenol chemical combination is provided
The method that object catalysis oxidation synthesizes benzoquinone compound, this method is using carbon materials such as onion carbon as heterogeneous catalysis, selectivity
Oxidation phenol class compound prepares benzoquinone compound, and process flow is simple, safe operation, environmental-friendly.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method of phenol compound catalysis oxidation synthesis benzoquinone compound, method includes the following steps:
(1) reactant phenol compound, solvent, solid catalyst and oxidant are added in reactor and are mixed, passed through
Ultrasonic treatment forms suspension；The molar ratio of the solid catalyst and phenol compound is (0.83~13.32): 1 is (excellent
Be selected as (6.66~13.32): 1), the molar ratio of the oxidant and phenol compound is (0.72~14.4): 1 (preferably
For (3.6~7.2): 1)；
(2) suspension obtained by step (1) is heated to 70~100 DEG C (preferably 75~100 DEG C) to react, when reaction
Between 2~16h；
(3) after reaction to step (2), reaction mixture is separated, obtains solid catalyst and remaining
Liquid mixture；
(4) liquid mixture obtained by step (3) is subjected to separating-purifying, obtains product benzoquinone compound.
In above-mentioned steps (1), the solid catalyst be onion carbon, active carbon, graphite, Nano diamond, graphene and
One or more of carbon nano-fiber；The solvent be dissolve each other with phenol compound used organic solvent (benzotrifluoride,
Acetonitrile, hexamethylene or methylene chloride)；The oxidant selects tert-butyl hydroperoxide.
The repeatable raw material as step (1) of separating obtained solid catalyst uses in last time step (3)；In step (4)
It is reusable that separating-purifying obtains remaining mother liquor and reaction raw materials after benzoquinone compound, that is, again returns to step after mixing
(1) in reactor.
Heretofore described phenol compound includes methylbenzene phenolic compound, and methylbenzene phenolic compound is 2,3,6-
Pseudocuminol, 2,3,5- pseudocuminol, 2,6- xylenol, 2,6 di t butyl phenol, 2,5- xylenol, 2-
Methylphenol or 2- methyl naphthols.It is corresponding benzoquinone compound by the reaction product of raw material of the phenol compound.
Design principle of the present invention is as follows:
Method of the invention is that phenol compound, solvent and solid catalyst are formed to suspension, and suspension heating adds
Enter a certain amount of tert-butyl hydroperoxide to be reacted as oxidant, then separating-purifying.The present invention is with tert-butyl hydroperoxide
For oxidant, using carbon materials such as onion carbon as the active component of heterogeneous catalysis, catalysis of phenol class compound oxidation reacts
Prepare corresponding benzoquinone compound.Non-metal carbon material is applied to the liquid phase oxidation system of phenol compound by the present invention for the first time
Have the reaction of the benzoquinone compound of high added value, and have very high activity and stability, changes previous to metal
The dependence of catalyst extends the application field of New Type of Carbon catalysis material.
Compared with prior art, the present invention having the following advantages:
1, using non-metal carbon material as catalyst, catalyst and product can be directly separated by filtration the present invention；The carbon simultaneously
Material has from a wealth of sources, environmental-friendly, chemical property stabilization, the advantages that can be recycled.In the selection of phenol compound
Property oxidation reaction in, the hydroxyl that oxidant is generated by thermal decomposition can capture the phenolic hydroxyl group on phenol, and to generate intermediate product benzene oxygen free
Base, and the defects of carbon material has the function of intermediate product benzene oxygen radical stable, avoids dimerization 1,4-benzoquinone class compound
Generation, improve the selectivity of corresponding benzoquinone compound.Wherein exist to the conversion ratio of different phenol compounds
99% or more, the selectivity of corresponding product benzoquinone compound is maintained between 67~82.5%.
2, reaction temperature of the present invention is lower, and reaction condition is mild, and operation is simple, and process is easy to control and repeats, no
It is related to strong acid and strong base, not only reduces the energy consumption in reaction process, also improves the safety coefficient of reaction.
3, non-metal carbons material Pyrogentisinic Acid's class compound oxidation such as onion carbon that the present invention uses belongs to heterogeneous reaction, instead
Answer activity higher, selectivity is preferably.
Detailed description of the invention
Fig. 1 is the product gas chromatogram of embodiment 1.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and embodiments.
Measurement and meter in relation to phenol compound conversion ratio (%) and benzoquinone compound selectivity (%) in embodiment
Calculation method (internal standard method) is as follows: after reaction reaches specified time, liquid-solid phase mixture is taken out from reaction vessel, was carried out to it
Conversion ratio and selectivity to determine reaction are analyzed obtained liquid phase mixture in filter.The analysis of product is being equipped with hair
It is carried out in the Agilent7890A gas-chromatography of buttress shaft.The testing conditions of gas chromatogram are as follows: 300 DEG C of sample injector, detector 280
DEG C, pillar uses temperature programming: then initial 110 DEG C of holdings 8min is raised to 230 DEG C with 20 DEG C/min, then keep 4min.Each reality
It applies in example and conventional separating-purifying is carried out to the liquid mixture after filtering solid catalyst to get corresponding product benzoquinones are arrived
Compound.Fig. 1 is the product gas chromatogram of embodiment 1.
Embodiment 1
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and is then sonicated to form suspension (time 5min).Wherein, benzotrifluoride
5ml, onion carbon and 2, the molar ratio of 3,6- trimethyl Pyrogentisinic Acids are 6.66:1.Oxidant rubs with 2,3,6- trimethyl Pyrogentisinic Acid's
You are than being 3.6:1.The mixing suspension is placed in oil bath pan is heated to 80 DEG C under agitation.After reaction 12 hours, from oil
Reaction vessel is taken out in bath, is cooled to room temperature, liquid-solid mixture is poured out, it is filtered, and obtains solid catalyst and is remained
Remaining liquid phase mixture is added a certain amount of internal standard (ethylbenzene), analyzes the liquid phase mixture, each in gas-chromatography
The retention time (Fig. 1) of substance is respectively as follows: tert-butyl alcohol 6.9min, benzotrifluoride 7.4min, 2,3,6- trimethyl 1,4-benzoquinone
9.91min, 2,3,6-TMP 9.98min, ethylbenzene 8.4min.The selectivity of 2,3,6- trimethyl 1,4-benzoquinone is according to internal standard
With the peak area of institute sample, obtained by the peak area of standard sample and the conversion rate conversion of 2,3,6-TMP.It calculates
Gained 2,3,6-TMP conversion ratio is 99.8%, and 2,3,6- trimethyl 1,4-benzoquinone are selectively 82.5%.
Embodiment 2
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and is then sonicated to form suspension (time 5min).Wherein, benzotrifluoride
The molar ratio of 5ml, onion carbon and 2,3,6-TMP is 6.66:1.The molar ratio of oxidant and 2,3,6- pseudocuminol
For 3.6:1.The mixing suspension is placed in oil bath pan is heated to temperature shown in table 1 under agitation.After reaction 12 hours,
Reaction vessel is taken out from oil bath pan, is cooled to room temperature, liquid-solid mixture is poured out, it is filtered, and obtains solid catalyst
With remaining liquid phase mixture, a certain amount of internal standard (ethylbenzene) is added, which is analyzed, measures 2,3,6- front threes
The conversion ratio of base phenol and 2,3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 1, it can be seen that and temperature raising is conducive to 2,3,
The oxidation of 6- pseudocuminol and 2,3,6- trimethyl 1,4-benzoquinone selectively produce, but when temperature is more than 80 DEG C, and 2,3,6- tri-
The selectivity of methyl-p-benzoquinone is begun to decline.
The influence that 1 reaction temperature of table reacts 2,3,6- oxidation of trimethylphenol
| Embodiment | 1 | 2-1 | 2-2 |
| Reaction temperature (DEG C) | 80 | 70 | 90 |
| 2,3,6- pseudocuminol conversion ratio (%) | 99.8 | 77.3 | 99.9 |
| 2,3,6- trimethyl 1,4-benzoquinone selectivity (%) | 82.5 | 63.9 | 74.8 |
Embodiment 3
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and forms suspension (time 5min) in ultrasonic treatment.Wherein, benzotrifluoride
The molar ratio of 5ml, onion carbon and 2,3,6-TMP is 6.66:1.The molar ratio of oxidant and 2,3,6- pseudocuminol
For 3.6:1.The mixing suspension is placed in oil bath pan is heated to 80 DEG C under agitation.Reaction time to table 2, from oil bath pan
Middle taking-up reaction vessel, is cooled to room temperature, pours out liquid-solid mixture, be filtered to it, obtains solid catalyst and remaining
Liquid phase mixture is added a certain amount of internal standard (ethylbenzene), analyzes the liquid phase mixture, measure 2,3,6-TMP
Conversion ratio and 2,3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 2, it can be seen that the extension time is conducive to 2,3,6- trimethyls
The oxidation of phenol and 2,3,6- trimethyl 1,4-benzoquinone selectively produce, but when the time is more than 12h, 2,3,6- trimethyl 1,4-benzoquinone
Selectivity begin to decline.
The influence that 2 reaction time of table reacts 2,3,6- oxidation of trimethylphenol
| Embodiment | 3-1 | 3-2 | 3-3 | 3-4 | 3-5 |
| Reaction time (h) | 2 | 4 | 8 | 12 | 16 |
| 2,3,6- pseudocuminol conversion ratio (%) | 85.3 | 89.1 | 99.8 | 99.8 | 99.9 |
| 2,3,6- trimethyl 1,4-benzoquinone selectivity (%) | 58.1 | 70.7 | 75.5 | 82.5 | 73.8 |
Embodiment 4
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and forms suspension (time 5min) in ultrasonic treatment.Wherein, benzotrifluoride
The molar ratio of 5ml, onion carbon and 2,3,6-TMP is 6.66:1.The molar ratio of oxidant and 2,3,6- pseudocuminol
As shown in table 3, which is placed in oil bath pan is heated to 80 DEG C under agitation.Reaction time 12h, from oil bath pan
Middle taking-up reaction vessel, is cooled to room temperature, pours out liquid-solid mixture, be filtered to it, obtains solid catalyst and remaining
Liquid phase mixture is added a certain amount of internal standard (ethylbenzene), analyzes the liquid phase mixture, measure 2,3,6-TMP
Conversion ratio and 2,3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 3, it can be seen that as the increase of oxidizer is conducive to
The oxidation of 2,3,6-TMP and 2,3,6- trimethyl 1,4-benzoquinone selectively produce, but work as oxidant and 2,3,6- front threes
When the molar ratio of base phenol is more than 3.6:1, the selectivity of 2,3,6- trimethyl 1,4-benzoquinone is begun to decline.
The influence that 3 oxidizer of table reacts 2,3,6- oxidation of trimethylphenol
| Embodiment | 4-1 | 4-2 | 4-3 | 4-4 | 4-5 |
| Oxidant and pseudocuminol molar ratio | 0.72 | 1.44 | 3.6 | 7.2 | 14.4 |
| 2,3,6- pseudocuminol conversion ratio (%) | 78.4 | 91.3 | 99.8 | 99.9 | 99.6 |
| 2,3,6- trimethyl 1,4-benzoquinone selectivity (%) | 70.3 | 77.2 | 82.5 | 58.3 | 30.4 |
Embodiment 5
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and forms suspension (time 5min) in ultrasonic treatment.Wherein, benzotrifluoride
The molar ratio of 5ml, onion carbon and 2,3,6-TMP is shown in Table 4.The molar ratio of oxidant and 2,3,6- pseudocuminol is
3.6:1, which is placed in oil bath pan is heated to 80 DEG C under agitation.Reaction time 12h, takes from oil bath pan
Reaction vessel out is cooled to room temperature, and pours out liquid-solid mixture, is filtered to it, and solid catalyst and remaining liquid phase are obtained
Mixture is added a certain amount of internal standard (ethylbenzene), analyzes the liquid phase mixture, measures the conversion of 2,3,6-TMP
Rate and 2,3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 4, it can be seen that as the increase of oxidizer is conducive to 2,3,
The oxidation of 6- pseudocuminol and 2,3,6- trimethyl 1,4-benzoquinone selectively produce, but when catalyst amount is more than 6.66:1
When, the selectivity of 2,3,6- trimethyl 1,4-benzoquinone is begun to decline.
The influence that 4 catalyst amount of table reacts 2,3,6- oxidation of trimethylphenol
| Embodiment | 5-1 | 5-2 | 5-3 | 5-4 | 5-5 |
| Catalyst and pseudocuminol molar ratio | 0.833 | 2.08 | 5.0 | 6.66 | 7.5 |
| 2,3,6- pseudocuminol conversion ratio (%) | 25.4 | 43.4 | 84.6 | 99.8 | 99.9 |
| 2,3,6- trimethyl 1,4-benzoquinone selectivity (%) | 60.3 | 71.2 | 77.5 | 82.5 | 80.4 |
Embodiment 6
By 0.1mmol 2,3,6- pseudocuminol and different solvents, solid catalyst onion carbon, oxidant tert-butyl mistake
Hydrogen oxide is added in closed glass container and mixes, and forms suspension (time 5min) in ultrasonic treatment.Wherein, solvent 5ml,
The molar ratio of onion carbon and 2,3,6- pseudocuminol is 6.66:1.The molar ratio of oxidant and 2,3,6- pseudocuminol is
3.6:1, which is placed in oil bath pan is heated to 80 DEG C under agitation.The solvent type that experiment uses every time is such as
Shown in table 5.Reaction time 12h, takes out reaction vessel from oil bath pan, is cooled to room temperature, and pours out liquid-solid mixture, carries out to it
Filtering, obtains solid catalyst and remaining liquid phase mixture, a certain amount of internal standard (ethylbenzene) is added, and carries out to the liquid phase mixture
Analysis, measures the conversion ratio and 2 of 2,3,6-TMP, 3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 5, it can be seen that
When benzotrifluoride is as solvent, the selectivity of the conversion ratio of 2,3,6-TMP and 2,3,6- trimethyl 1,4-benzoquinone is best.
The influence that 5 reaction dissolvent of table reacts 2,3,6- oxidation of trimethylphenol
| Embodiment | 1 | 6-1 | 6-2 | 6-3 |
| Solvent | Benzotrifluoride | Acetonitrile | Methylene chloride | Hexamethylene |
| 2,3,6- pseudocuminol conversion ratio (%) | 99.8 | 81.9 | 48.1 | 98.8 |
| 2,3,6- trimethyl 1,4-benzoquinone selectivity (%) | 82.5 | 38.1 | 50.1 | 74.7 |
Embodiment 7
By 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst, oxidant tert-butyl hydroperoxide
It is added in closed glass container and mixes, form suspension (time 5min) in ultrasonic treatment.Wherein, solvent 5ml, catalyst
Molar ratio with 2,3,6- pseudocuminol is 6.66:1.The molar ratio of oxidant and 2,3,6-TMP is 3.6:1, should
Mixing suspension is placed in oil bath pan is heated to 80 DEG C under agitation.The carbon material catalyst type that experiment uses every time is such as
Shown in table 6.Reaction time 12h, takes out reaction vessel from oil bath pan, is cooled to room temperature, and pours out liquid-solid mixture, carries out to it
Filtering, obtains solid catalyst and remaining liquid phase mixture, a certain amount of internal standard (ethylbenzene) is added, and carries out to the liquid phase mixture
Analysis, measures the conversion ratio and 2 of 2,3,6-TMP, 3,6- trimethyl 1,4-benzoquinone selectively the results are shown in Table 6.Analyze data
Best 2,3,6- pseudocuminol conversion ratio and 2,3,6- trimethyl are showed when can obtain onion carbon as catalyst to benzene
Quinone selectivity.
The influence that the different carbon material catalyst of table 6 react 2,3,6- oxidation of trimethylphenol
Embodiment 8
(1) by 0.1mmol 2,3,6- pseudocuminol and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl
Hydrogen peroxide is added in closed glass container and mixes, and forms suspension (time 5min) in ultrasonic treatment.Wherein, fluoroform
The molar ratio of benzene 5ml, onion carbon and 2,3,6-TMP is 6.66:1.Mole of oxidant and 2,3,5- pseudocuminol
Than for 3.6:1.The mixing suspension is placed in oil bath pan is heated to 80 DEG C under agitation.After reaction 12 hours, from oil bath
Reaction vessel is taken out in pot, is cooled to room temperature, pours out liquid-solid mixture, it is filtered, obtain solid catalyst and residue
Liquid phase mixture, a certain amount of internal standard (ethylbenzene) is added, which is analyzed.
(2) the solid catalyst onion carbon obtained after step (1) filtering is cleaned and dried, then makees the onion carbon
It for catalyst, is reacted again under the same conditions with step (1), measures conversion ratio and selectivity with identical method.
So this catalyst circulation is used seven times, measured result is shown in Table 7.After reusing seven times, 2,3,6-TMP conversion
Rate and the variation of the selectivity of 2,3,6- trimethyl 1,4-benzoquinone less, illustrate that onion carbon is can be recycled, so as to reduce
The cost of catalyst.
7 catalyst stability experimental result of table
Embodiment 9
By 0.1mmol phenol compound and benzotrifluoride, solid catalyst onion carbon, oxidant tert-butyl hydroperoxide
It is added in closed glass container and mixes, form suspension (time 5min) in ultrasonic treatment.Phenol used is tested every time
The type of compound is shown in Table 8.Wherein, benzotrifluoride 5ml, onion carbon are 6.66~13.32 from the molar ratio of different methylphenols:
1.Oxidant is 3.6:1 from the molar ratio of different methylphenols.The mixing suspension is placed in oil bath pan to be added under agitation
Heat is to 75~100 DEG C.After reaction 4~12 hours, reaction vessel is taken out from oil bath pan, is cooled to room temperature, liquid is poured out and mixes admittedly
Object is filtered it, obtains solid catalyst and remaining liquid phase mixture, a certain amount of internal standard (ethylbenzene) is added, to the liquid
Phase mixture is analyzed.The conversion ratio for the variety classes phenol compound measured is selected with corresponding benzoquinone compound
Property the results are shown in Table 8 under the experiment condition of optimization, it can be seen that when onion carbon is as catalyst, to different types of phenol
Class compound and corresponding benzoquinone compound show preferable conversion ratio and selectivity, and it is very strong to illustrate that the catalyst has
Universality.
Influence of the 8 onion carbon of table to variety classes methylphenol oxidation reaction
The above are preferred embodiments of the present invention, but protection content of the invention is not limited to the above embodiment, and are not carrying on the back
From under the spirit and scope of inventive concept, various changes and advantages that will be apparent to those skilled in the art are all included in the present invention
In.
Claims (7)
1. a kind of method of phenol compound catalysis oxidation synthesis benzoquinone compound, it is characterised in that: this method include with
Lower step:
(1) reactant phenol compound, solvent, solid catalyst and oxidant are added in reactor and are mixed, through ultrasound
Processing forms suspension；The molar ratio of the solid catalyst and phenol compound is (0.83~13.32): 1, the oxygen
The molar ratio of agent and phenol compound is (0.72~14.4): 1；The solid catalyst is onion carbon, nanometer Buddha's warrior attendant
One or more of stone, graphene and carbon nano-fiber；The solvent is benzotrifluoride, acetonitrile, hexamethylene or methylene chloride；
The oxidant selects tert-butyl hydroperoxide；
(2) suspension obtained by step (1) is heated to 70~100 DEG C to react, 2~16h of reaction time；
(3) after reaction to step (2), reaction mixture is separated, obtains solid catalyst and remaining liquid
Mixture；
(4) liquid mixture obtained by step (3) is subjected to separating-purifying, obtains product benzoquinone compound.
2. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1, feature exist
In: in step (1), the molar ratio of the solid catalyst and phenol compound is (6.66~13.32): 1.
3. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1, feature exist
In: in step (1), the molar ratio of the oxidant and phenol compound is (3.6~7.2): 1.
4. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1, feature exist
In: in step (2), reaction temperature is 75~100 DEG C.
5. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1, feature exist
In: separating obtained solid catalyst repeats that the raw material of step (1) is used as to use in step (3)；Separating-purifying obtains in step (4)
Remaining mother liquor is mixed with reaction raw materials back in step (1) reactor after product.
6. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1, feature exist
It include methylbenzene phenolic compound in: the phenol compound, methylbenzene phenolic compound is 2,3,6-TMP, 2,
3,5- pseudocuminol, 2,6- xylenol, 2,6 di t butyl phenol, 2,5- xylenol, 2- methylphenol or 2-
Methyl naphthols.
7. the method for phenol compound catalysis oxidation synthesis benzoquinone compound according to claim 1 or 6, feature
It is: is corresponding benzoquinone compound by the reaction product of raw material of the phenol compound.
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| Carbon nanotubes as catalysts for catalytic wet peroxide oxidation of highly concentrated phenol solutions: towards process intensification;M.T.Pinho et al.;《Applied Catalysis B: Environmental》;20141101;第165卷;706-714 * |
| Graphite and Carbon black materials as catalysts for wet peroxide oxidation;C. M. Dominguez et al.;《Applied Catalysis B: Environmental》;20130809;第144卷;599-606 * |
| Reaction network and kinetic modeling of wet oxidation of phenolcatalyzed by activated carbon;A.Santos et al.;《Chemical Engineering Science》;20051222;第61卷;2457-2467 * |
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