CN111116321A - Green synthesis method for preparing phenol by benzene hydroxylation - Google Patents

Green synthesis method for preparing phenol by benzene hydroxylation Download PDF

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CN111116321A
CN111116321A CN202010068247.2A CN202010068247A CN111116321A CN 111116321 A CN111116321 A CN 111116321A CN 202010068247 A CN202010068247 A CN 202010068247A CN 111116321 A CN111116321 A CN 111116321A
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benzene
catalyst
oxide
mor
hydrogen peroxide
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CN111116321B (en
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王平
余昊轩
楚庆岩
商芳芳
杨海玉
刁统贺
王鸣
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Shandong University of Technology
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention belongs to the field of fine organic chemical industry, and particularly relates to a green synthesis method for preparing phenol by benzene hydroxylation. Benzene and hydrogen peroxide react in an organic solvent and a catalyst to obtain phenol after the reaction; wherein: the catalyst is a metal oxide loaded mesoporous or macroporous catalyst, the catalyst framework is a titanium-silicon molecular sieve, and the metal oxide is copper oxide, zinc oxide, iron oxide, molybdenum oxide, manganese oxide, aluminum oxide, vanadium oxide or cobalt oxide. The method has the advantages of simple process, high selectivity, environmental protection and no pollution, the catalyst can be recycled, higher phenol purity and conversion rate can be obtained in a shorter time than the prior art, the preparation process and the process are environment-friendly, and the atomic economic synthesis concept is met; the product purity is more than or equal to 99.5 percent, and the product yield can reach 65 percent.

Description

Green synthesis method for preparing phenol by benzene hydroxylation
Technical Field
The invention belongs to the field of fine organic chemical industry, and particularly relates to a green synthesis method for preparing phenol by benzene hydroxylation.
Background
Phenol is one of the main raw materials used in chemical production, and is mainly used for synthesizing phenolic resin, bactericides, preservatives and medicines. At present, more than 90% of phenol in the world is produced by a three-step cumene process, but the phenol is large in energy consumption, low in atom utilization rate, large in acetone amount of a byproduct and not in accordance with a sustainable development concept. The method for preparing phenol by directly oxidizing benzene with hydrogen peroxide has the advantages of short route, high atom economy, no by-product and the like, and is considered to be a clean production method which is the most promising method for replacing the cumene method.
In order to solve the defects, a plurality of patents have been technically improved, and CN200810226203 discloses a catalyst for preparing phenol by benzene hydroxylation and a preparation method and application thereof: the method comprises the steps of dropwise adding a Cu + Al cross-linking agent and a copper metal salt into diluted clay suspension by taking clay as a carrier, and carrying out ion exchange to obtain a catalyst for benzene hydroxylation reaction, wherein the phenol conversion rate is 64.2%, and the selectivity is 85.1%. CN102228833A discloses a cobalt-containing porous material and application thereof in direct hydroxylation of benzene to prepare phenol, wherein a long-chain organic amine is adopted as a template agent, a hydrothermal method is adopted to prepare a Co-containing porous inorganic material, the catalytic performance of a catalyst on the reaction of oxidizing benzene by hydrogen peroxide to prepare phenol is examined, and the yield of phenol is 28%. CN102294272A discloses a catalyst for preparing phenol by benzene hydroxylation and a preparation method thereof, which is an organic-inorganic dual-modified phosphomolybdovanadophosphoric acid Cs2.5(MIMPS)nH1.5-nPMo11VO40The catalytic hydrogen peroxide oxidizes benzene to prepare phenol, and the yield of phenol is 17 percent.
In addition, Gao et al supported copper oxide as an active component on modified Tianan red clay to achieve a benzene conversion of 14.1%. Cu/VO prepared from Guxiangfeng subject groupx-Ti-O2The yield and selectivity of phenol are 25.6% and 92% respectively by the composite catalyst. The Cu/SBA-1 catalyst is synthesized by utilizing a sol-gel method, such as the plum pine and the like, under the optimal catalyst condition, the benzene conversion rate is 48.5%, but the phenol selectivity is only 47%. CuFe oxide synthesized by Makglane and Ray is used for catalyzing that the conversion rate of phenol reaches 44 percent and the selectivity of the phenol reaches 91 percent. The Fe-based catalyst based on the Fenton reaction mechanism is also synthesized, and shows good catalytic performance in the reaction of preparing phenol by oxidizing benzene with hydrogen peroxide. Arab et al treated Fe3O4The catalyst is loaded on the ordered mesoporous carbon material, the catalytic performance of the catalyst on the preparation of phenol by oxidizing benzene with hydrogen peroxide is considered, and the yield of phenol reaches 16.6%. Zhao Pinna, et al, by combining p-xylene based diimidazole ionic liquids [ Pxydim]Cl2Polyoxometallate H with V-substituted Keggin structure5PMo10V2O40Combining to prepare the self-assembled mesoporous polyoxometallate ion hybrid catalyst Pxydim]2.5MoV2When the method is used for the reaction of preparing phenol from benzene, the yield can reach 29.7 percent.
However, the above catalysts have problems of complicated preparation process and low conversion rate and selectivity. Therefore, the development of the high-efficiency catalyst which is simple in preparation method and can be recycled has important significance for researching the reaction for preparing phenol by directly hydroxylating benzene.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green synthesis method for preparing phenol by benzene hydroxylation, which can obtain higher phenol purity and conversion rate in a shorter time than the prior art, has green and environment-friendly preparation process and accords with the atomic economic synthesis concept; the product purity and yield are high.
The invention relates to a green synthesis method for preparing phenol by benzene hydroxylation, which comprises the steps of reacting benzene and hydrogen peroxide in an organic solvent and a catalyst to obtain phenol after reaction; wherein: the catalyst is a metal oxide loaded mesoporous or macroporous catalyst, the catalyst framework is a titanium-silicon molecular sieve, and the metal oxide is copper oxide, zinc oxide, iron oxide, molybdenum oxide, manganese oxide, aluminum oxide, vanadium oxide or cobalt oxide.
The synthetic route is as follows:
Figure BDA0002376581370000021
wherein:
the source of the metal oxide is one of metal chloride, metal hydroxide and metal nitrate.
The reaction temperature is 30-80 ℃, and the reaction time is 60-240 min. The concentration of hydrogen peroxide is 27.5-50%, the molar ratio of hydrogen peroxide to benzene is 1: 1-8: 1. preferably, the reaction temperature is 70 ℃ and the reaction time is 120 min; the concentration of hydrogen peroxide is 30%, the molar ratio of hydrogen peroxide to benzene is 3: 1, under the preferable conditions, the product purity and the yield are high.
The organic solvent is one or more of methanol, ethanol, propanol, isopropanol, toluene, DMSO, tert-butanol, acetone, butanone, acetic acid, water or acetonitrile. Preferably, the organic solvent is acetic acid and acetonitrile in a volume ratio of 1:1, the product purity and yield are high by adopting the mixed solvent.
The mass ratio of the metal oxide to the titanium silicalite molecular sieve is 0.05: 1-0.5: 1; the dosage of the catalyst is 1-15% of the mass of benzene, and the molar ratio of the benzene to the organic solvent is 1: 1-1: 50.
The catalyst of the invention is a metal oxide loaded mesoporous or macroporous catalyst, and the preparation method of the catalyst comprises the following steps: calcining the hydrogen mordenite in HNO3Carrying out medium reflux acid washing, carrying out suction filtration washing to neutrality, and drying to obtain a deep dealumination sample; taking the obtained deep dealuminization sample, placing the deep dealuminization sample in a quartz tube reactor, and drying the deep dealuminization sample at 390-400 ℃ with N2Pre-treatment in the stream, then passing N2Fluidizing TiCl4The vapor is carried into the reactor for reaction and pure N is used2Washing at the same temperature to remove residual TiCl from the zeolite powder4(ii) a In N2After the mixture is cooled to room temperature, washing the treated sample by deionized water, and drying to obtain MOR type titanium silicate Ti-MOR; adding ammonium metavanadate aqueous solution and cobalt acetate aqueous solution into the obtained MOR type titanium silicate Ti-MOR, uniformly dispersing by ultrasonic wave, and dryingThe catalyst was dried overnight and calcined at 540 ℃ and 560 ℃ to obtain a Co/V-Ti-MOR catalyst.
The catalyst adopted by the invention is a metal oxide loaded mesoporous or macroporous catalyst, preferably a macroporous catalyst, and the pore size of the microporous molecular sieve catalyst is equal to or smaller than that of benzene, so that reactant molecules are diffused in the pore, approach to a titanium active site and reaction products are diffused from the inside to the outside of the pore and are subjected to serious steric hindrance effect. The Co/V-Ti-MOR catalyst prepared by the invention is a macroporous catalyst, and the ten-membered ring channels of the catalyst have no restriction on the steric hindrance of benzene, so that the conversion rate and the selectivity of phenol are higher.
As a preferred technical scheme, the preparation method of the catalyst comprises the following steps: calcining hydrogen-type mordenite at 600 + -10 deg.C for 9-11h, and adding HNO 5.5-6.5mol/L with solid-to-liquid ratio of 1:103Carrying out medium reflux acid washing for 5-7h, carrying out suction filtration washing to neutrality, and drying to obtain a deep dealumination sample; taking the obtained deep dealuminization sample, placing the deep dealuminization sample in a quartz tube reactor, and drying the deep dealuminization sample at 390-400 ℃ with N2Pre-treating for 1.8-2.2h in the flow, and then passing through N2Fluidizing TiCl4Introducing the steam into the reactor, reacting for 3.5-4.0h, and adding pure N2Washing at the same temperature for 0.8-1.0 hr to remove residual TiCl from zeolite powder4(ii) a In N2After cooling to room temperature, washing the treated sample with deionized water, and drying in air at 55-65 ℃ overnight to obtain MOR type titanium silicate Ti-MOR; adding an ammonium metavanadate aqueous solution and a cobalt acetate aqueous solution into the obtained MOR type titanium silicate Ti-MOR, uniformly dispersing for 10-15min by ultrasonic waves, drying overnight at 42-48 ℃, heating to 540-560 ℃ at a heating rate of 1.0-1.1 ℃/min, and calcining for 6-7h to obtain a Co/V-Ti-MOR catalyst; wherein: the mass ratio of ammonium metavanadate, cobalt acetate and MOR type titanium silicate Ti-MOR is 46: 42: 50.
as a preferred technical scheme, the green synthesis method for preparing phenol by benzene hydroxylation, provided by the invention, comprises the steps of putting a Co/V-Ti-MOR catalyst, acetic acid, acetonitrile and benzene into a reaction bottle, uniformly mixing, carrying out oil bath at a constant temperature, controlling the temperature at 70 ℃, dropwise adding 30 wt% hydrogen peroxide into the two flasks, stirring and reacting, setting the dropping speed of the hydrogen peroxide to be 0.2g/min, reacting for 120min, and stopping the reaction to obtain phenol; wherein: the feeding ratio of the Co/V-Ti-MOR catalyst, acetic acid, acetonitrile and benzene is as follows: 0.5: 4: 4: 0.78, the molar ratio of the benzene to the hydrogen peroxide is 1: 3.
compared with the prior art, the invention has the following advantages:
the invention provides a green synthesis method for preparing phenol by benzene hydroxylation, which has the advantages of simple process, high selectivity, greenness, no pollution, recyclable catalyst, higher phenol purity and conversion rate in a shorter time than the prior art, green and environment-friendly preparation process and process, and accordance with an atom economy synthesis concept; the product purity is more than or equal to 99.5 percent, and the product yield can reach 65 percent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Calcining hydrogen-type mordenite at 600 deg.C for 10 hr, and adding HNO at 6.0mol/L with solid-to-liquid ratio of 1:103Carrying out medium reflux acid washing for 6.0h, carrying out suction filtration washing to neutrality, and drying to obtain a deep dealumination sample; taking the obtained deep dealuminization sample, placing the deep dealuminization sample in a quartz tube reactor, and drying the deep dealuminization sample at 400 ℃ with N2Pretreated for 2.0h in stream, then passed through N2Fluidizing TiCl4The steam is brought into the reactor to react for 4.0h and then pure N is used2Washing at the same temperature for 1.0h to remove residual TiCl from the zeolite powder4(ii) a In N2After cooling to room temperature, the treated sample was washed with deionized water and dried overnight in air at 60 ℃ to obtain MOR type Ti-MOR. Adding an ammonium metavanadate aqueous solution (containing 0.46g of ammonium metavanadate) and a cobalt acetate aqueous solution (containing 0.42g of cobalt acetate) into 0.5g of MOR type titanosilicate Ti-MOR, uniformly dispersing for 12min by ultrasonic waves, drying overnight at 45 ℃, heating to 550 ℃ at a heating rate of 1.0 ℃/min, and calcining for 6.0h to obtain the Co/V-Ti-MOR catalyst.
0.5g of the Co/V-Ti-MOR catalyst, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene are put into a 50mL two-mouth reaction bottle with condensation reflux and magnetic stirring and are uniformly mixed, oil bath is carried out at constant temperature, and the temperature is controlled at 70 ℃. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: the molar ratio of hydrogen peroxide is 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 65 percent, and the selectivity is more than or equal to 99.5 percent.
(the embodiment is the optimum condition)
Example 2
Taking the MOR type titanium silicate Ti-MOR obtained in the example 1 as a carrier, adding 0.0163g of ammonium metavanadate aqueous solution under slow stirring, uniformly dispersing in an ultrasonic bath for 10min after completely mixing, putting into an oven, drying overnight at 45 ℃, then heating to 550 ℃ at a heating rate of 1 ℃/min, calcining for 6h, and finally obtaining the V-Ti-MOR catalyst.
0.5g of the V-Ti-MOR catalyst, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene are put into a 50mL two-mouth reaction bottle with condensing reflux and magnetic stirring and mixed evenly, and oil bath is carried out at constant temperature and the temperature is controlled at 70 ℃. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 23 percent, and the selectivity is more than or equal to 99.5 percent.
Example 3
Taking 0.5g of TS-1 as a carrier, adding 0.0163g of ammonium metavanadate aqueous solution under slow stirring, uniformly dispersing in an ultrasonic bath for 10min after completely mixing, putting into an oven, drying overnight at 45 ℃, then heating to 550 ℃ at a heating rate of 1 ℃/min, and calcining for 6h to obtain the V-TS-1 catalyst.
0.5g of the V-TS-1 catalyst, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene are put into a 50mL two-mouth reaction bottle with condensation reflux and magnetic stirring and mixed evenly, and oil bath is carried out at constant temperature, and the temperature is controlled at 70 ℃. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 17 percent, and the selectivity is more than or equal to 99.5 percent.
Example 4
Taking 0.5g of Ti-Beta as a carrier, adding 0.0163g of ammonium metavanadate aqueous solution under slow stirring, uniformly dispersing in an ultrasonic bath for 10min after completely mixing, putting into an oven, drying overnight at 45 ℃, heating to 550 ℃ at a heating rate of 1 ℃/min, and calcining for 6h to finally obtain the V-Ti-Beta catalyst.
0.5g of the V-Ti-Beta catalyst, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene are put into a 50mL two-mouth reaction bottle with condensing reflux and magnetic stirring to be uniformly mixed, and oil bath is carried out at constant temperature, and the temperature is controlled at 70 ℃. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 8 percent, and the selectivity is more than or equal to 99.5 percent.
Example 5
Taking 0.5g of Ti-MCM-41 as a carrier, adding 0.0163g of ammonium metavanadate aqueous solution under slow stirring, uniformly dispersing in an ultrasonic bath for 10min after completely mixing, putting into an oven, drying overnight at 45 ℃, heating to 550 ℃ at a heating rate of 1 ℃/min, and calcining for 6h to finally obtain the V-Ti-MCM-41 catalyst.
0.5g of the V-Ti-MCM-41 catalyst, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene are put into a 50mL two-mouth reaction bottle with condensing reflux and magnetic stirring to be uniformly mixed, and oil bath is carried out at constant temperature, and the temperature is controlled at 70 ℃. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 11 percent, and the selectivity is more than or equal to 99.5 percent.
Example 6
1g of the Co/V-Ti-MOR catalyst prepared in example 1, 8mL of acetone and 0.78g of benzene were put into a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1:1, stirring and reacting at 70 ℃ for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 25 percent, and the selectivity is more than or equal to 99.5 percent.
Example 7
1g of the Co/V-Ti-MOR catalyst prepared in example 1, 8mL of tert-butanol and 0.78g of benzene were placed in a 50mL two-necked reaction flask with reflux condenser and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: and 5, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 5 percent, and the selectivity is more than or equal to 99.5 percent.
Example 8
1g of the Co/V-Ti-MOR catalyst prepared in example 1, 8mL of acetonitrile and 0.78g of benzene were put into a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 10.5 percent, and the selectivity is more than or equal to 99.5 percent.
Example 9
1g of the Co/V-Ti-MOR catalyst prepared in example 1, 8mL of acetic acid and 0.78g of benzene were placed in a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at 70 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 16.3 percent, and the selectivity is more than or equal to 99.5 percent.
Example 10
0.5g of the Co/V-Ti-MOR catalyst prepared in example 1, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene were put into a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at the temperature of 60 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 52 percent, and the selectivity is more than or equal to 99.5 percent.
Example 11
0.5g of the Co/V-Ti-MOR catalyst prepared in example 1, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene were put into a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: 3, stirring the mixture at the temperature of 80 ℃ for reaction for 120min, terminating the reaction, sampling and analyzing, wherein the conversion rate is 60.4 percent, and the selectivity is more than or equal to 99.5 percent.
Example 12
0.5g of the Co/V-Ti-MOR catalyst prepared in example 1, 4mL of acetic acid, 4mL of acetonitrile and 0.78g of benzene were put into a 50mL two-necked reaction flask with reflux condensation and magnetic stirring and mixed uniformly, and the temperature was controlled at 70 ℃ in an oil bath at a constant temperature. Thereafter, hydrogen peroxide (30 wt%) was added dropwise to the two-necked flask using a peristaltic pump at a dropping rate of 0.2 g/min. Wherein, benzene: hydrogen peroxide (molar ratio) 1: and 3, after stirring and reacting for 60min at 70 ℃, terminating the reaction, sampling and analyzing, wherein the conversion rate is 27 percent, and the selectivity is more than or equal to 99.5 percent.

Claims (10)

1. A green synthesis method for preparing phenol by benzene hydroxylation is characterized by comprising the following steps: benzene and hydrogen peroxide react in an organic solvent and a catalyst to obtain phenol after the reaction; wherein: the catalyst is a metal oxide loaded mesoporous or macroporous catalyst, the catalyst framework is a titanium-silicon molecular sieve, and the metal oxide is copper oxide, zinc oxide, iron oxide, molybdenum oxide, manganese oxide, aluminum oxide, vanadium oxide or cobalt oxide.
2. The green synthesis process for the hydroxylation of benzene to produce phenol according to claim 1, wherein: the reaction temperature is 30-80 ℃, and the reaction time is 60-240 min.
3. The green synthesis process for the hydroxylation of benzene to produce phenol according to claim 1, wherein: the concentration of hydrogen peroxide is 27.5-50%, the molar ratio of hydrogen peroxide to benzene is 1: 1-8: 1.
4. a green synthesis process for the hydroxylation of benzene to produce phenol according to claim 3, characterized by: the reaction temperature is 70 ℃, and the reaction time is 120 min; the concentration of hydrogen peroxide is 30%, the molar ratio of hydrogen peroxide to benzene is 3: 1.
5. the green synthesis process for the hydroxylation of benzene to produce phenol according to claim 1, wherein: the organic solvent is one or more of methanol, ethanol, propanol, isopropanol, toluene, DMSO, tert-butanol, acetone, butanone, acetic acid, water or acetonitrile.
6. The green synthesis process of benzene hydroxylation to produce phenol according to claim 5, characterized by: the organic solvent is acetic acid and acetonitrile according to the volume ratio of 1:1 and mixing.
7. The green synthesis process for the hydroxylation of benzene to produce phenol according to claim 1, wherein: the mass ratio of the metal oxide to the titanium silicalite molecular sieve is 0.05: 1-0.5: 1; the dosage of the catalyst is 1-15% of the mass of benzene, and the molar ratio of the benzene to the organic solvent is 1: 1-1: 50.
8. The green synthesis process for the hydroxylation of benzene to produce phenol according to claim 1, wherein: the preparation method of the catalyst comprises the following steps: calcining the hydrogen mordenite in HNO3Carrying out medium reflux acid washing, carrying out suction filtration washing to neutrality, and drying to obtain a deep dealumination sample; taking the obtained deep dealuminization sample, placing the deep dealuminization sample in a quartz tube reactor, and drying the deep dealuminization sample at 390-400 ℃ with N2Pre-treatment in the stream, then passing N2Fluidizing TiCl4The vapor is carried into the reactor for reaction and pure N is used2Washing at the same temperature to remove residual TiCl from the zeolite powder4(ii) a In N2Cooling to room temperature, washing with deionized water to obtainDrying the sample to obtain MOR type titanium silicate Ti-MOR; adding an ammonium metavanadate aqueous solution and a cobalt acetate aqueous solution into the obtained MOR type titanium silicate Ti-MOR, uniformly dispersing by ultrasonic waves, drying overnight, and calcining at the temperature of 540-.
9. The green synthesis process of benzene hydroxylation to produce phenol according to claim 8, characterized by: the preparation method of the catalyst comprises the following steps: calcining hydrogen-type mordenite at 600 + -10 deg.C for 9-11h, and adding HNO 5.5-6.5mol/L with solid-to-liquid ratio of 1:103Carrying out medium reflux acid washing for 5-7h, carrying out suction filtration washing to neutrality, and drying to obtain a deep dealumination sample; taking the obtained deep dealuminization sample, placing the deep dealuminization sample in a quartz tube reactor, and drying the deep dealuminization sample at 390-400 ℃ with N2Pre-treating for 1.8-2.2h in the flow, and then passing through N2Fluidizing TiCl4Introducing the steam into the reactor, reacting for 3.5-4.0h, and adding pure N2Washing at the same temperature for 0.8-1.0 hr to remove residual TiCl from zeolite powder4(ii) a In N2After cooling to room temperature, washing the treated sample with deionized water, and drying in air at 55-65 ℃ overnight to obtain MOR type titanium silicate Ti-MOR; adding an ammonium metavanadate aqueous solution and a cobalt acetate aqueous solution into the obtained MOR type titanium silicate Ti-MOR, uniformly dispersing for 10-15min by ultrasonic waves, drying overnight at 42-48 ℃, heating to 540-560 ℃ at a heating rate of 1.0-1.1 ℃/min, and calcining for 6-7h to obtain a Co/V-Ti-MOR catalyst; wherein: the mass ratio of ammonium metavanadate, cobalt acetate and MOR type titanium silicate Ti-MOR is 46: 42: 50.
10. a green synthesis process for the hydroxylation of benzene to produce phenol according to any of claims 1-9, characterized by: placing a Co/V-Ti-MOR catalyst, acetic acid, acetonitrile and benzene into a reaction bottle, uniformly mixing, carrying out oil bath at a constant temperature, controlling the temperature to be 70 ℃, dropwise adding 30 wt% hydrogen peroxide into the two-neck flask, stirring and reacting, setting the dropping speed of the hydrogen peroxide to be 0.2g/min, and stopping the reaction for 120min to obtain phenol; wherein: the feeding ratio of the Co/V-Ti-MOR catalyst, acetic acid, acetonitrile and benzene is as follows: 0.5: 4: 4: 0.78, the molar ratio of the benzene to the hydrogen peroxide is 1: 3.
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