CN106831352A - A kind of method of the direct phenol processed of dioxygen oxidation benzene - Google Patents
A kind of method of the direct phenol processed of dioxygen oxidation benzene Download PDFInfo
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- 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
- C07C37/58—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 molecular oxygen
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Abstract
The method that the present invention discloses a kind of direct phenol processed of dioxygen oxidation benzene, including following reactions steps：During the catalyst of precise, auxiliary agent, benzene, reaction dissolvent successively added into reactor, to being passed through oxidant in reactor, it is characterised in that catalyst is the mixture of carbon nitrogen polymer and vanadium-containing compound；Auxiliary agent is alkali metal salt；Reaction dissolvent is acetic acid aqueous solution；Oxidant is oxygen.The present invention uses oxygen as oxidant, cheap and easy to get, environmental sound；Method for preparing catalyst is simple, stable in catalytic performance；Graphite ene-type carbonitride activates phenyl ring, and miscellaneous many phosphomolybdic acid choline salt activating oxygens, the two synergy makes the step of benzene one be converted into phenol under conditions of being participated in without reducing agent；Phenol yield is up to 10.7%, phenol selectivity>99%（Based on GC analysis results）；Catalyst is after the completion of reaction solid, and convenient recovery is reused.
Description
Technical field
The present invention relates to phenol preparation field, and in particular to a kind of method of the direct phenol processed of dioxygen oxidation benzene.
Background technology
Phenol is important Organic Chemicals, mainly uses its synthesis of bisphenol A, caprolactam, phenolic resin, and various
Pharmaceutical intermediate.
The industrially prepared mainly cumene method of current phenol, the method reactions steps are more, and high energy consumption, intermediate product is explosive
Fried, seriously polluted, while the cheap acetone of by-product, these are its unsurmountable shortcomings.Therefore phenol by directly hydroxylating benzene
New Process show its superiority and importance.
The oxidant used by the benzene hydroxylation phenol system of research mainly divides both at home and abroad N2O、H2O2And O2.Compared to
N2O and H2O2, O2With nontoxic, cheap and easy to get advantage, it is considered to be optimal oxidant.
O2Oxybenzene phenol system has two kinds：Gas-solid phase reaction system and liquid-phase reaction system.Gas-solid phase reaction body
The reaction temperature of system is universal higher, and the selectivity of target product phenol is not universal high.The O of liquid-phase system2Oxidation Benzene to phenol ratio
Gas-solid phase system reaction temperature is low, and mild condition, phenol selectivity is higher.
Benzene and O2It is relatively stable, the two more difficult direct reaction within the temperature range of liquid-phase reaction system, therefore, it is most of
It has been reported that research in sacrificial reducing agent be essential.Sacrificial reducing agent includes H2, CO, ascorbic acid and zinc powder
Deng.The use of these sacrificial reducing agents increased the danger of reaction, improve reaction cost.Therefore participated in without reducing agent
Liquid phase O2Oxybenzene phenol reactant system is ideal.
Passoni（J MolCatal A:Chem,1997,120:117-123）Report use " acid chloride+miscellaneous many containing vanadium
Acid " [Pd (OAc)2+PMoVx, x=0,2.6,3.3,4.5] catalyst system and catalyzing, be solvent with second aqueous acid（HOAc and H2O's
Mol ratio is 1:2）, lithium acetate（LiOAc）It is additive, 130 °C of reaction temperature, reaction time 4h, the conversion ratio of benzene is 15%,
The selectivity of phenol is 70% or so（I.e. phenol yield is about 10.5%）.There is no the ginseng of sacrificial reducing agent in this reaction system
With, but acid chloride is noble metal series catalysts, it is relatively costly.
Gao（KinetCatal,2010,51(3):394-397）With chain alkyl amine as template, closed by hydro-thermal method
Into sheet VOx, it is solvent with acetic acid, reducing agent is not added additionally, in 0.1g catalyst, the reaction condition of 150 °C and 10h
Under, 3.7% phenol yield can be obtained（Based on 1mL, about 11mmol benzene.The temperature of this reaction system is higher, the reaction time compared with
Long, phenol yield is relatively low.
The content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides the side that a kind of direct hydroxylating of dioxygen oxidation benzene prepares phenol
Method, the method by the use of oxygen as oxygen source, the mixture of carbon nitrogen polymer and vanadium-containing compound as catalyst, with alkali metal salt
As co-catalyst, benzene direct hydroxylating phenol with high selectivity is realized under conditions of being participated in without reducing agent.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of method of the direct phenol processed of dioxygen oxidation benzene, including following reactions steps：By the catalyst of precise, auxiliary agent,
Benzene, reaction dissolvent are successively added in reactor, and to oxidant is passed through in reactor, the catalyst is for carbon nitrogen polymer and containing vanadium
The mixture of compound；The auxiliary agent is alkali metal salt；The reaction dissolvent is acetic acid aqueous solution；The oxidant is oxygen.
Preferably, the reaction temperature of the reaction is 100-125 DEG C, and the reaction time is 2-5.5 hours.
Preferably, the carbon nitrogen polymer is graphite ene-type carbonitride.
Preferably, the vanadium-containing compound is miscellaneous many phosphomolybdic acid choline salts of Transition Metals V substitution.
Preferably, the mass ratio of carbon nitrogen polymer and vanadium-containing compound is 1 in the catalyst:15-7:15, the polymerization of carbon nitrogen
Thing is 1 with the mass ratio of benzene:28-195.
Preferably, the alkali metal salt is lithium acetate.
Preferably, the oxygen pressure is 0.5MPa-2.5MPa.
Preferably, the volume fraction of the acetic acid aqueous solution is 20%-80%.
Preferably, the alkali metal salt and the mass ratio of benzene are 1:5-40.
Beneficial effects of the present invention have：
1st, oxygen is cheap and easy to get as oxidant, environmental sound；
2nd, method for preparing catalyst is simple, stable in catalytic performance；
3rd, graphite ene-type carbonitride activation phenyl ring, miscellaneous many phosphomolybdic acid choline salt activating oxygens, the two synergy, without reducing agent
The step of benzene one is set to be converted into phenol under conditions of participation；
4th, phenol yield is up to 10.7%, phenol selectivity>99%（Based on GC analysis results）；
5th, catalyst is after the completion of reaction solid, and convenient recovery is reused.
Specific embodiment
The present invention by the use of oxygen as oxygen source, the mixture of carbon nitrogen polymer and vanadium-containing compound as catalyst, with alkali
Slaine realizes benzene direct hydroxylating phenol with high selectivity as co-catalyst under conditions of being participated in without reducing agent.
It is of the invention it is critical that prepare the mechanism of phenol from dioxygen oxidation benzene hydroxylation, reaction is divided into phenyl ring
Activation and two parts process of oxygen activating transfer.It is anti-that this brand-new reaction mechanism causes that dioxygen oxidation benzene hydroxylation prepares phenol
Should smoothly occur in the case where being participated in without reducing agent, more effectively promote the step conversion of benzene into phenol.Meanwhile, catalysis
Agent is still after the reaction solid, facilitates utilization and recycle.
Method of the present invention, it is characterised in that use using oxygen as oxidant, acetic acid aqueous solution is molten as reaction
Used as catalyst, alkali metal salt is auxiliary agent to the mixture of agent, carbon nitrogen polymer and vanadium-containing compound, and reaction temperature is 100-125
DEG C, reacting 2-2.5 hours, benzene is oxidized to phenol with high selectivity.
Oxygen pressure is 0.5MPa-2.5MPa；Acetic acid aqueous solution volume fraction is 20%-80%；Carbon nitrogen polymer is graphite
Ene-type carbonitride（g-C3N4）, vanadium-containing compound is miscellaneous many phosphomolybdic acid choline salts of Transition Metals V substitution（Ch5PMoV2）, the two
Mixture be catalyst, g-C3N4And Ch5PMoV2Mass ratio be 1:15-7:15）, g-C3N4It is 1 with the mass ratio of benzene:
28-195。
Auxiliary agent is one or more in lithium acetate, sodium acetate or potassium acetate, is preferably lithium acetate, itself and benzene
Mass ratio is 1:5-40.
The present invention is to be achieved by the following measures：
Graphite ene-type carbonitride used by the present invention（g-C3N4）With melamine as raw material, preparation method is referring to document
（Langmuir, 2009, 25 ：10397–10401）；Vanadium-containing compound is miscellaneous many phosphomolybdic acid choline of Transition Metals V substitution
Salt（Ch5PMoV2）Preparation method is referring to document（Appl. Catal. B:Environ. 2013,138:161-166）；The two is pressed
According to mass ratio g-C3N4: Ch5PMoV2=1:15-7:15 grind uniform in mortar.
The process of phenol by directly hydroxylating benzene：By the catalyst of precise, auxiliary agent, 5mmol substrate benzene and 2mL
Acetic acid aqueous solution is successively added in 10 mL high pressure stainless steel cauldrons, O2Purge and sealed reactor, then pass to 0.5-
The O of 2.5MPa2, stirring is opened, reaction is started when temperature of reaction kettle rises to 100-125 °C, reaction is stopped after 2-5.5h.Add
Isosorbide-5-Nitrae-dioxane as internal standard, with gas chromatograph GC analysis of Phenol yields.
Specific embodiment：
Embodiment 1：
In 10ml reactors, miscellaneous many phosphomolybdic acid choline salts that the 0.03g catalyst Transition Metals V of precise is replaced
（Ch5PMoV2）, 0.06 g auxiliary agent lithium acetates, in 2 ml acetic acid aqueous solutions of addition（50%）, add substrate benzene 0.39g（5mmol）,
Oxygen charged pressure is 2.0MPa, is reacted at 120 DEG C, is reacted by after 1-24h, phenol yield is respectively less than 0.2%.
Embodiment 2：
In 10ml reactors, by the 0.01g catalyst graphite ene-type carbonitrides of precise（g-C3N4）, 0.06g auxiliary agent second
Sour lithium, in addition 2ml acetic acid aqueous solutions（50%）, add substrate benzene 0.39g（5mmol）, oxygen charged pressure is 2.0MPa,
120 DEG C are reacted, and are reacted by after 1-24h, phenol yield is respectively less than 0.2%.
Embodiment 3：
In 10ml reactors, by the 0.01g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4:Ch5PMoV2=1:3）, 0.06g auxiliary agent second
Sour lithium, in addition 2ml acetic acid aqueous solutions（50%）, add substrate benzene 0.39g（5mmol）, oxygen charged pressure is 2.0MPa,
120 DEG C are reacted, and are reacted after 4.5, and phenol yield is up to 8.9%.
Embodiment 4：
In 10ml reactors, by the 0.012g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）, 0.06 g auxiliary agents
Lithium acetate, in addition 2ml acetic acid aqueous solutions（50%）, add substrate benzene 0.39g（5mmol）, oxygen charged pressure is 2.0MPa,
Reacted at 120 DEG C, reacted after 4.5, phenol yield is up to 10.7%.
Embodiment 5：
In 10ml reactors, by the 0.012g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）Add 2ml acetic acid
In the aqueous solution（50%）, 0.06g auxiliary agent lithium acetates are weighed respectively（LiOAc）, sodium acetate（NaOAc）And potassium acetate（KOAc）Add
In reactor, substrate benzene 0.39g is added（5mmol）, oxygen charged pressure is 2.0MPa, is reacted at 120 DEG C, and reaction is passed through
4.5h。
The influence of the different alkali metal salt auxiliary agent Pyrogentisinic Acid's yields of table 1
| Auxiliary agent | LiOAc | NaOAc | KOAc |
| Phenol yield（%） | 10.7 | 8.4 | 6.5 |
Table 1 illustrates lithium acetate as auxiliary agent to reacting most favourable.
Embodiment 6：
In 10ml reactors, by the 0.042g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）Add 2 ml second
In aqueous acid（50%）, weigh respectively in auxiliary agent lithium acetate 0g, 0.02g, 0.04g, 0.06g, 0.08g addition reactor, add
Substrate benzene 0.39g（5mmol）, oxygen charged pressure is 2.0MPa, is reacted at 120 DEG C, is reacted by 4.5h.
The influence of the auxiliary agent lithium acetate consumption Pyrogentisinic Acid's yield of table 2
| Auxiliary agent lithium acetate consumption（g） | 0 | 0.02 | 0.04 | 0.06 | 0.08 |
| Phenol yield（%） | 2.2 | 3.8 | 7.6 | 10.7 | 8.3 |
The explanation addition lithium acetate of table 2 can significantly improve phenol yield, and 0.06g lithium acetate consumptions are optimal.
Embodiment 7：
The influence of 3 reaction time of table Pyrogentisinic Acid's yield
| Reaction time（h） | 3.5 | 4.0 | 4.5 | 5.0 |
| Phenol yield（%） | 6.8 | 7.8 | 10.7 | 6.2 |
In 10ml reactors, by the 0.042g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）, 0.06 g auxiliary agents
Lithium acetate, in addition 2ml acetic acid aqueous solutions（50%）, add substrate benzene 0.39g（5mmol）, oxygen charged pressure is 2.0MPa,
3.5h, 4.0h, 4.5h, 5h are reacted respectively at 120 DEG C.
The explanation of table 3 reaction time 4.5h is optimal, and extension reaction time phenol yield declines.
Embodiment 8：
In 10ml reactors, by the 0.042g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With Transition Metals V
Miscellaneous many phosphomolybdic acid choline salts of substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）, 0.06 g auxiliary agents
Lithium acetate, in 2 ml acetic acid aqueous solutions of addition（50%）, add substrate benzene 0.39g（5mmol）, oxygen charged pressure is
2.0MPa, reaction 4.5h is carried out at 120 DEG C.Solid catalyst is recovered by centrifugation after reaction, it is so heavy for the second secondary response
Multiple operation, carries out four secondary responses altogether.
The utilization and recycle of the catalyst of table 4 is investigated
| Reaction times（h） | 1 | 2 | 3 | 4 |
| Phenol yield（%） | 10.7 | 8.6 | 7.1 | 5.9 |
The utilization and recycle of the explanation catalyst of table 4 is preferable.
In 10ml reactors, by the 0.012g catalyst graphite ene-type carbonitrides of precise（g-C3N4）With transition gold
Miscellaneous many phosphomolybdic acid choline salts of category vanadium substitution（Ch5PMoV2）Mixture（Mass ratio g-C3N4: Ch5PMoV2=2:5）Add 2ml
In the acetic acid aqueous solution of various concentrations, 0.06g auxiliary agent lithium acetates are weighed（LiOAc）Add in reactor, add substrate benzene 0.39g
（5mmol）, oxygen charged pressure is 2.0MPa, is reacted at 120 DEG C, is reacted by 4.5h.
The influence of acetic acid concentration Pyrogentisinic Acid's yield in the acetic acid aqueous solution of table 5
| Acetic acid concentration（V%） | 20 | 40 | 50 | 60 | 80 |
| Phenol yield（%） | 0.2 | 4.1 | 8.9 | 5.7 | 2.4 |
Acetic acid concentration is 50% best results in the explanation acetic acid aqueous solution of table 5.
The above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method of the direct phenol processed of dioxygen oxidation benzene, including following reactions steps：Catalyst, auxiliary agent, benzene, reaction is molten
Agent is successively added in reactor, to being passed through oxidant in reactor, it is characterised in that the catalyst is carbon nitrogen polymer and contains
The mixture of vfanadium compound；The auxiliary agent is alkali metal salt；The reaction dissolvent is acetic acid aqueous solution；The oxidant is oxygen
Gas.
2. the method for the direct phenol processed of a kind of dioxygen oxidation benzene according to claim 1, it is characterised in that the reaction
Reaction temperature is 100-125 DEG C, and the reaction time is 2-5.5 hours.
3. the method for the direct phenol processed of a kind of dioxygen oxidation benzene according to claim 1, it is characterised in that the carbon nitrogen gathers
Compound is graphite ene-type carbonitride.
4. the method for the direct phenol processed of a kind of dioxygen oxidation benzene according to claim 1, it is characterised in that described containing vanadium
Compound is miscellaneous many phosphomolybdic acid choline salts of Transition Metals V substitution.
5. a kind of method of the direct phenol processed of dioxygen oxidation benzene according to claim 1, it is characterised in that the catalyst
The mass ratio of middle carbon nitrogen polymer and vanadium-containing compound is 1:15-7:15, carbon nitrogen polymer is 1 with the mass ratio of benzene:28-195.
6. a kind of method of the direct phenol processed of dioxygen oxidation benzene according to claim 1, it is characterised in that the alkali metal
Salt be lithium acetate, sodium acetate or potassium acetate in one or more.
7. a kind of method of the direct phenol processed of dioxygen oxidation benzene according to claim 1, it is characterised in that the oxygen pressure
Power is 0.5MPa-2.5MPa.
8. a kind of method of the direct phenol processed of dioxygen oxidation benzene according to claim 1, it is characterised in that the acetic acid water
The volume fraction of solution is 20%-80%.
9. a kind of method of the direct phenol processed of dioxygen oxidation benzene according to claim 1, it is characterised in that the alkali metal
Salt is 1 with the mass ratio of benzene:5-40.
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| CN110183308A (en) * | 2019-05-30 | 2019-08-30 | 陕西科技大学 | A kind of non-metallic catalyst, preparation method and application preparing phenol for benzene direct oxidation |
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- 2016-12-19 CN CN201611177031.XA patent/CN106831352A/en active Pending
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| CN110183308A (en) * | 2019-05-30 | 2019-08-30 | 陕西科技大学 | A kind of non-metallic catalyst, preparation method and application preparing phenol for benzene direct oxidation |
| CN110183308B (en) * | 2019-05-30 | 2022-03-25 | 陕西科技大学 | Nonmetal catalyst for preparing phenol by directly oxidizing benzene, preparation method and application |
| CN110372508A (en) * | 2019-07-16 | 2019-10-25 | 复旦大学 | A kind of environment-friendly preparation method thereof of ethyl pyruvate |
| CN110372508B (en) * | 2019-07-16 | 2022-06-21 | 复旦大学 | Green preparation method of ethyl pyruvate |
| CN113683488A (en) * | 2021-08-09 | 2021-11-23 | 三峡大学 | Preparation method of 4,4' -dihydroxybiphenyl |
| CN113683488B (en) * | 2021-08-09 | 2023-08-25 | 三峡大学 | Preparation method of 4,4' -dihydroxybiphenyl |
| CN114105734A (en) * | 2021-11-19 | 2022-03-01 | 浙江工业大学 | Method for continuous flow synthesis of 2-chloro hydroquinone |
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Application publication date: 20170613 |