CN105712846B - A kind of method that catalyst benzene hydroxylation prepares phenol - Google Patents

A kind of method that catalyst benzene hydroxylation prepares phenol Download PDF

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CN105712846B
CN105712846B CN201410742365.1A CN201410742365A CN105712846B CN 105712846 B CN105712846 B CN 105712846B CN 201410742365 A CN201410742365 A CN 201410742365A CN 105712846 B CN105712846 B CN 105712846B
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catalyst
benzene
ferrocene
phenol
graphene oxide
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CN105712846A (en
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高爽
尚森森
王连月
赵公大
杨华
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • 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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a kind of method that catalyst benzene hydroxylation prepares phenol, wherein, catalyst is ferrocene grafted amino group silane oxidation graphene, add graphene oxide into toluene, ultrasound, in a nitrogen atmosphere, amino silane is added, at 25~100 DEG C, reacts 12h~24h, washing, dry, obtained material is scattered in ethanol, under the conditions of 25~80 DEG C, ferrocene carboxaldehyde stirring reaction 6h~24h is added, adds sodium cyanoborohydride (NaBH3CN), stirring reaction 12h~72h, solid will be obtained and washed with ether, obtain catalyst；By obtained catalyst and benzene, acetonitrile, H2O2Mixing, under the conditions of 25~80 DEG C, stirring 4h obtains phenol, and the present invention on stannic oxide/graphene nano page by being grafted ferrocene, by graphene oxide to the adsorption activation and ferrocene of benzene to H2O2Activation, greatly improve benzene hydroxylation catalyst system and catalyzing activity, reaction condition is gentle, catalyst material stable performance.

Description

A kind of method that catalyst benzene hydroxylation prepares phenol
Technical field
The invention belongs to benzene hydroxylation to prepare phenol field, specifically provides a kind of catalyst benzene hydroxylation and prepares phenol Method.
Background technology
Phenol is a kind of important chemical intermediate, can be used for produce bisphenol-A, phenolic resin, dyestuff, antioxidant with And medicine etc..At present, phenol whole world demand is close to 1,000 ten thousand tons, and the demand of China Pyrogentisinic Acid accounts for world's aggregate demand 10%.The traditional production method of phenol is cumene method, and 95% phenol is produced by this method in the world at present.In this method, The hydrolysis of isopropylbenzene needs substantial amounts of inorganic acid, brings certain environmental problem；Simultaneously again can be by co-product acetone market Restrict.Especially in overall process, the phenol total recovery based on benzene feedstock only has 5%.Therefore, no matter from the angle of sustainable development Or Atom economy considers, people are intended to the method aoxidized by green catalysis always, and the step of direct oxidation benzene one prepares benzene Phenol.But in benzene hydroxylation reaction, benzene feedstock property is stable, it is difficult to it is oxidized, meanwhile, phenol product property is active, easily A major challenge that phenol is always field of catalytic chemistry is produced in the further oxidative degradation of generation, therefore, benzene direct oxidation, especially Research using molecular oxygen as the benzene direct oxidation phenol of oxygen source is considered as one of great difficult problem of current catalytic field always.
With H2O2It is it is intended that substitution cumene method route production phenol to the direct liquid phase oxidation phenol of benzene for oxidant Another route.By the use of H2O2 as oxidant, its unique accessory substance is H2O, Atom economy is high, and environment is not polluted, It is a kind of environment-friendly cleaning oxidizer.Phenol relative to benzene be easier aoxidize generation catechol, hydroquinones, benzoquinones and The accessory substances such as tar, so as to cause to react low selectivity.After HTS comes out, Perego etc. uses it for being catalyzed benzene first Phenol synthesizes.Subsequent Thangaraj etc. reports H2O2 as oxidant titanium molecular sieve catalysis Benzene to phenol.People also attempt to use (APTS)/MCM-41 of VO2+ functionalization, LaMn-MCM-41, Co (V, Nb, La)-MCM-41and Fe/ activated carbon are catalyst Obtain benzene conversion ratio 50-65%, and H2O2Selectivity is only 17-50%.But existing benzene hydroxylation reaction system efficiency is very low. The present invention on stannic oxide/graphene nano page by being grafted ferrocene, adsorption activation and ferrocene by graphene oxide to benzene To H2O2Activation, greatly improve benzene hydroxylation catalyst system and catalyzing activity.
Using stannic oxide/graphene nano page grafting ferrocene material benzene hydroxylation field at present there is no literature reported on.
The content of the invention
In view of the above-mentioned problems, the purpose of the present invention is a kind of preparation for the catalyst that phenol is prepared for benzene hydroxylation of exploitation Method, specially a kind of preparation method for the ferrocene grafted amino group silane-graphene oxide for being catalyzed benzene hydroxylation phenol.
The technical scheme is that：
Catalyst is ferrocene grafted amino group silane-graphene oxide, is prepared by the following method, by graphene oxide plus Enter in toluene, ultrasonic 6h~24h, under nitrogen atmosphere protection, add amino silane, at 25~100 DEG C, reaction 12h~ 24h, then washed with ethanol, dry, obtained material is scattered in ethanol, under the conditions of 25~80 DEG C, add ferrocene first Aldehyde stirring reaction 6h~24h, adds sodium cyanoborohydride (NaBH3CN), stirring reaction 12h~72h, solid is obtained, used For ether washing and filtering to filtrate clear, it is the catalyst that phenol is prepared for benzene hydroxylation to obtain product；
By obtained catalyst and benzene, acetonitrile, mass fraction 30%~50% oxidant H2O2Mixing, in 25~80 DEG C Under the conditions of, 4h is stirred, obtains phenol.
The mass volume ratio of graphene oxide and toluene is 2.5g/L.
Prepare in catalyst process, ultrasonic electrical power is 200W~600W, and ultrasonic time is preferably 12h~16h.
Amino silane is 3- TSL 8330s (APTMS) or APTES One or both of (APTES).
Prepare in catalyst process, after adding amino silane, is carried out to graphene oxide excellent the amido modified reaction time Elect 15h~20h as.
The mass ratio of graphene oxide and amino silane is 1:2~1:10, preferably 1:4~1:7, amino silane and two cyclopentadienyl Iron formaldehyde mole ratio is 5:1~1:5, ferrocene carboxaldehyde and NaBH3CN mol ratios are 2:1~1:6.
In catalyst benzene hydroxylation prepares phenol reactant, Fe and benzene mole ratio are 1 in catalyst:1000~1:50.
In catalyst benzene hydroxylation prepares phenol reactant, oxidant H2O2It is 1 with benzene mole ratio:10~10:1.
In catalyst benzene hydroxylation prepares phenol reactant, mass fraction of the acetonitrile in system is 55.8%.
Beneficial effects of the present invention are：
The present invention on stannic oxide/graphene nano page by being grafted ferrocene, the adsorption activation by graphene oxide to benzene And ferrocene is to H2O2Activation, greatly improve benzene hydroxylation catalyst system and catalyzing activity, reaction condition is gentle, catalyst Material property is stable, meets green, the requirement of environmental protection.
Brief description of the drawings
Fig. 1 is ferrocene grafted amino group silane-graphene oxide composite material of gained low resolution (left side) is low and resolution ratio The TEM on (right side).
Embodiment
Describe the specific implementation step of the present invention in detail below by some embodiments, should not be by these embodiments as this Invention scope limits.
Embodiment 1
1000mg graphene oxides are taken to be added in 400ml toluene, after ultrasound (ultrasonic electrical power 400W) 12h, in N2Protect Shield is lower to add 4.0mlAPTMS backflow 24h, dries 12h after the APTMS of its physical absorption is washed off with a large amount of ethanol under 80 degree. Above-mentioned APTMS grafted graphene oxides are dispersed in 250ml ethanol, and add the lower stirring of 100 degree of 33mmol ferrocene carboxaldehydes 24h, add 44mmol NaBH3CN continues stirring 3 days, and gained solid ether washs 3 days in apparatus,Soxhlet's afterwards, Finally give black solid 620mg.
Reacted using obtained catalysis material for benzene hydroxylation, by 80mg catalyst, 0.78g benzene (10mmol), 6.8mL Acetonitrile, 3.4g 30%H2O2, add in 25mL flasks and react, magnetic agitation, reaction temperature is 60 DEG C, keeps 2h, obtains phenol Yield is 14.3%.
Embodiment 2
1000mg graphene oxides are taken to be added in 400ml toluene, after ultrasound (ultrasonic electrical power 400W) 14h, in N2Protect Shield is lower to add 6.0mlAPTMS backflow 24h, dries 12h after the APTMS of its physical absorption is washed off with a large amount of ethanol under 80 degree. Above-mentioned APTMS grafted graphene oxides are dispersed in 250ml ethanol, and add the lower stirring of 80 degree of 22mmol ferrocene carboxaldehydes 24h, add 33mmol NaBH3CN continues stirring 3 days, and gained solid ether washs 3 days in apparatus,Soxhlet's afterwards, Finally give black solid 560mg.
Reacted using obtained catalysis material for benzene hydroxylation, by 80mg catalyst, 0.78g benzene (10mmol), 6.8mL Acetonitrile, 3.4g 30%H2O2, add in 25mL flasks and react, magnetic agitation, reaction temperature is 80 DEG C, keeps 2h, obtains phenol Yield is 13.1%.
Embodiment 3
Take 1000mg graphene oxides to be added in 400ml toluene, after ultrasound (ultrasonic electrical power 400W) 16h, protected in N2 Shield is lower to add 7.0mlAPTMS backflow 24h, dries 12h after the APTMS of its physical absorption is washed off with a large amount of ethanol under 80 degree. Above-mentioned APTMS grafted graphene oxides are dispersed in 250ml ethanol, and add 60 times stirring 24h of 44mmol ferrocene carboxaldehydes, Add 22mmol NaBH3CN continues stirring 3 days, and gained solid ether washs 3 days in apparatus,Soxhlet's afterwards, finally Obtain black solid 570mg.
Reacted using obtained catalysis material for benzene hydroxylation, by 80mg catalyst, 0.78g benzene (10mmol), 6.8mL Acetonitrile, 3.4g 30%H2O2, add in 25mL flasks and react, magnetic agitation, reaction temperature is 40 DEG C, keeps 1h, obtains phenol Yield is 11.2%.
Embodiment 4-10
Similar to embodiment 1, it is different from part and is：Ultrasonic time, amino silane species and dosage, ferrocene carboxaldehyde Dosage, NaBH3 (CN) and reaction temperature, react the following result (table one) after terminating：
Table one
Embodiment 11-15
Similar to embodiment 1, it is different from part and is：Using different amino silanes, amino silane and ferrocene carboxaldehyde Mol ratio, ferrocene carboxaldehyde and NaBH3(CN) mol ratio, reaction temperature obtain following result (table two)：
Table two

Claims (10)

1. a kind of method that catalyst benzene hydroxylation prepares phenol, it is characterised in that：Catalyst is ferrocene grafted amino group Silane-graphene oxide, is prepared by the following method, is added graphene oxide into toluene, ultrasonic 6h~24h, in nitrogen gas Under atmosphere protection, amino silane is added, at 25~100 DEG C, reacts 12h~24h, then is washed with ethanol, is dried, the thing that will be obtained Matter is scattered in ethanol, under the conditions of 25~80 DEG C, is added ferrocene carboxaldehyde stirring reaction 6h~24h, is added cyano group boron hydrogen Change sodium (NaBH3CN), stirring reaction 12h~72h, solid is obtained, the use of ether washing and filtering to filtrate is clear, obtains Product is the catalyst that phenol is prepared for benzene hydroxylation；
By obtained catalyst and benzene, acetonitrile, mass fraction 30%~50% oxidant H2O2Mixing, in 25~80 DEG C of conditions Under, stirring 2-8h obtains phenol.
2. according to the method for claim 1, it is characterised in that：The mass volume ratio of graphene oxide and toluene is 1.25- 5g/L。
3. according to the method for claim 1, it is characterised in that：Prepare in catalyst process, ultrasonic electrical power be 200W~ 400W, ultrasonic time are preferably 12h~16h.
4. according to the method for claim 1, it is characterised in that：Amino silane is 3- TSL 8330s Or one or both of APTES (APTES) (APTMS).
5. according to the method for claim 1, it is characterised in that：Prepare in catalyst process, after adding amino silane, to oxygen The graphite alkene progress amido modified reaction time is preferably 15h~20h.
6. according to the method for claim 1, it is characterised in that：The mass ratio of graphene oxide and amino silane is 1:2~ 1:10, amino silane is 5 with ferrocene carboxaldehyde mol ratio:1~1:5, ferrocene carboxaldehyde and NaBH3CN mol ratios are 2:1~1: 6。
7. according to the method for claim 1, it is characterised in that：The mass ratio of graphene oxide and amino silane is 1:4~ 1:7。
8. according to the method for claim 1, it is characterised in that：In catalyst benzene hydroxylation prepares phenol reactant, Fe and benzene mole ratio are 1 in catalyst:1000~1:50.
9. according to the method for claim 1, it is characterised in that：In catalyst benzene hydroxylation prepares phenol reactant, Oxidant H2O2It is 1 with benzene mole ratio:10~10:1.
10. according to the method for claim 1, it is characterised in that：In catalyst benzene hydroxylation prepares phenol reactant, Mass fraction of the acetonitrile in system is 25-100%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2794729C1 (en) * 2022-02-11 2023-04-24 Общество С Ограниченной Ответственностью "Би Ай Технолоджи" Method for obtaining phenol from benzene

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WO2014144352A2 (en) * 2013-03-15 2014-09-18 Mackinac Polymers Llc Polymeric composition with electroactive characteristics

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2794729C1 (en) * 2022-02-11 2023-04-24 Общество С Ограниченной Ответственностью "Би Ай Технолоджи" Method for obtaining phenol from benzene

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