CN116178112A - Ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method and application - Google Patents
Ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method and application Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000010936 titanium Substances 0.000 title claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 49
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 48
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 239000011541 reaction mixture Substances 0.000 claims abstract description 29
- 239000000523 sample Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 238000000527 sonication Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 abstract description 13
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- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 6
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- 230000000052 comparative effect Effects 0.000 description 14
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- 238000004458 analytical method Methods 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 11
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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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
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- 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
Abstract
The invention discloses an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, which comprises the following steps: phenol hydroxylation reaction is carried out under stirring conditions, phenol is firstly dissolved in methanol, then TS-1 titanium silicalite molecular sieve catalyst is added, and the reaction temperature is slowly increased to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 The solution was gradually added to the reaction mixture and stirring was continued for 6h at normal pressure, and when the reaction temperature was raised to 60 ℃, the ultrasonic operation was immediately added. An ultrasonic assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method. The method utilizes the cavitation effect of ultrasonic waves to greatly slow down the carbon deposition condition in the phenol hydroxylation reaction process of the TS-1 titanium silicalite molecular sieve, prolongs the service life of the catalyst and reduces the cost of the reaction flow. The whole reaction process can not be carried outThe method has the advantages of causing extra waste discharge, saving cost and being a method with great industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of molecular sieve preparation, and in particular relates to an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method and application.
Background
The titanium-silicon molecular sieve is a special molecular sieve containing titanium atoms in a molecular sieve framework, the titanium-silicon molecular sieve TS-1 with an MFI topological structure is synthesized for the first time in 1983 by Tramasso, and the titanium-silicon molecular sieve TS-1 has high thermal stability, acid resistance, hydrophobicity and good catalytic activity and selectivity, and particularly has a unique shape-selective catalytic function on liquid-phase oxidation reactions (such as alkane oxidation, alkene epoxidation, alcohol oxidation, hydroxylation of benzene and phenol, ketone ammoximation and the like) of various organic matters taking industrial hydrogen peroxide as an oxidant under the conditions of low temperature and normal pressure.
The benzenediol, including catechol and hydroquinone, is an important chemical raw material and is widely applied to industries such as medicines, pesticides, dyes and the like. The natural yield of the benzenediol is very small and is difficult to meet the social requirement, so the benzenediol produced by the artificial synthesis method has higher practical value. Phenol is used as a raw material, hydrogen peroxide is used as an oxidant, catechol and hydroquinone are directly generated by one-step oxidation, the method is a main flow process for producing the benzenediol at present, and most of the catechol and nearly 40% of the hydroquinone in the world are produced by the method.
Phenol hydroxylation is a typical series of reactions, and related researches show that catechol and benzenediol are condensed to generate viscous carbon substances such as phenol tar and the like in the phenol hydroxylation process. The deactivation of the fresh titanium silicalite molecular sieve is mainly caused by the coverage of the inner surface area and pore channels of the molecular sieve by reaction process products such as phenol tar.
At present, a regeneration method of roasting an inactivated catalyst at a high temperature is generally adopted to recover the activity of the catalyst, such as methods of patent publications CN201810978223.3 and CN 202210553108.8. In the case of titanium-silicon molecular sieve catalysts, it is difficult to achieve the requirement of recovering the catalyst activity by simple high-temperature roasting regeneration treatment. Because the organic matters in the pore channels can damage the structure at local positions at high temperature due to intense heat release when the organic matters are directly roasted in the air, and the molecular sieve is required to be switched when the organic matters are frequently roasted, so that the mechanical strength of the molecular sieve is easy to be reduced and the molecular sieve is easy to be pulverized. In addition, the method can also be used for washing the solvent, such as the patent publications CN202110544816.0 and CN202011158094.7, but the solvent consumption in the whole regeneration process is large, and the cost is additionally increased. Even if the ultrasonic regenerated molecular sieve is adopted, as shown in patent publication CN201510118201.6, the problem that the circulation times of the molecular sieve catalyst are not high due to carbon deposition blockage in the phenol hydroxylation process is not changed. Therefore, how to slow down the carbon deposition rate during the phenol hydroxylation reaction becomes an important way to reduce the production cost.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method and application.
The technical scheme adopted for solving the technical problems is as follows:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
phenol hydroxylation reaction is carried out under stirring conditions, phenol is firstly dissolved in methanol, then TS-1 titanium silicalite molecular sieve catalyst is added, and the reaction temperature is slowly increased to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 The solution was gradually added to the reaction mixture, phenol and H 2 O 2 The molar ratio of (2) is 3:1, stirring is continued for 6 hours under normal pressure, when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 5-8W/mL, the frequency is 10-20 KHz, and the interval ratio is 1: 3-1: and 5, the treatment time is 10-40 min, and the ultrasonic probe is arranged at the middle position of the liquid.
Further, the conditions of the ultrasound are: the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid.
Further, the mass ratio of the TS-1 titanium silicalite molecular sieve catalyst to phenol is 1:10 to 1:15.
further, the method comprises the following steps:
phenol hydroxylation is carried out under stirring conditions by first dissolving phenol in methanol, phenol: ratio of methanol g: mL is 1: and 6, adding a TS-1 titanium silicalite molecular sieve catalyst, wherein the mass ratio of the added catalyst to the mass of phenol is 1:10. slowly increasing the reaction temperature to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 Gradually adding phenol and H to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring continuously for 6 hours under normal pressure; when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 40min, and the ultrasonic probe is arranged at the middle position of the liquid.
Further, the sonication was performed for 1 second, for 5 seconds, which is one sonication cycle.
The application of the method in prolonging the service life of the TS-1 titanium silicalite molecular sieve.
The invention has the advantages and positive effects that:
1. according to the method, the carbon deposition process of phenol hydroxylation on the titanium-silicon molecular sieve TS-1 is researched, and the ultrasonic operation is added in the reaction process, so that the service life of the phenol hydroxylation reaction of the TS-1 titanium-silicon molecular sieve can be prolonged to more than 3 times. The ultrasonic operation under the intensity can not damage the framework structure of the molecular sieve, and solves the problems of high energy consumption in the traditional process, structural strength reduction caused by a series of regeneration processes such as frequent unloading and calcination in the process, and the like, which are observed by a transmission electron microscope picture (figure 1). And the whole regeneration process does not need strong acid and alkali treatment, is energy-saving and environment-friendly, and greatly simplifies the steps of the whole regeneration process. Compared with the traditional reaction process, the method has the advantages of slow reduction speed of the phenol conversion rate along with the cycle times (figure 2), easy control of process parameters, simple operation, easy control, low cost and high yield.
2. The method of the invention utilizes the cavitation effect of ultrasonic waves to greatly slow down the carbon deposition condition in the phenol hydroxylation reaction process of the TS-1 titanium silicalite molecular sieve. The ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation reaction method provided by the invention can slow down the carbon deposition condition in the phenol hydroxylation reaction process, prolong the service life of the catalyst and reduce the cost of the reaction flow. The whole reaction process can not cause extra waste discharge, saves the cost, and is a method with great industrial application prospect.
Drawings
FIG. 1 is a transmission electron micrograph of an ultrasonic TS-1 titanium silicalite molecular sieve according to the present invention;
FIG. 2 is a graph of phenol conversion versus operating conditions in accordance with the present invention;
FIG. 3 is a graph comparing results of ultrasound and ultrasound-free thermogravimetry in accordance with the present invention;
FIG. 4 is a transmission electron micrograph of a titanium silicalite molecular sieve according to the present invention under ultrasound conditions TS-1 in excess of the present invention.
Detailed Description
The following describes the embodiments of the present invention in detail, but the present embodiments are illustrative and not limitative, and are not intended to limit the scope of the present invention.
The raw materials used in the invention are conventional commercial products unless specified; the methods used in the present invention are conventional in the art unless otherwise specified.
An ultrasonic assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method is characterized in that: the method comprises the following steps:
phenol hydroxylation reaction is carried out under stirring conditions, phenol is firstly dissolved in methanol, then TS-1 titanium silicalite molecular sieve catalyst is added, and the reaction temperature is slowly increased to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 The solution was gradually added to the reaction mixture, phenol and H 2 O 2 The molar ratio of (2) is 3:1, stirring is continued for 6 hours under normal pressure, when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 5-8W/mL, the frequency is 10-20 KHz, and the interval ratio is 1: 3-1: and 5, the treatment time is 10-40 min, and the ultrasonic probe is arranged at the middle position of the liquid.
Preferably, the conditions of the ultrasound are: the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid.
Preferably, the mass ratio of the TS-1 titanium silicalite molecular sieve catalyst to phenol is 1:10 to 1:15.
preferably, the method comprises the steps of:
phenol hydroxylation is carried out under stirring conditions by first dissolving phenol in methanol, phenol: ratio of methanol g: mL is 1: and 6, adding a TS-1 titanium silicalite molecular sieve catalyst, wherein the mass ratio of the added catalyst to the mass of phenol is 1:10. slowly increasing the reaction temperature to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 Gradually adding phenol and H to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring continuously for 6 hours under normal pressure; when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 40min, and the ultrasonic probe is arranged at the middle position of the liquid.
Preferably, the sonication is for 1 second and for 5 seconds, this being one sonication cycle.
The application of the method in prolonging the service life of the TS-1 titanium silicalite molecular sieve.
Specifically, the relevant preparation and detection examples are as follows:
the gas chromatography conditions in the present invention can be as follows,
TABLE 1 gas chromatography conditions
TABLE 2 thermogravimetric analysis conditions
The detection step of the transmission electron microscope photograph in fig. 1: transmission electron microscopy is the most intuitive method of characterizing pore structure. The experiment adopts JEOLJEM-2100 field emission transmission electron microscopy instrument of Japanese Hitachi to characterize the pore channel structure characteristics of the prepared sample. The highest working voltage can reach 200kV, and the high-resolution transmission electron microscope characterization can be performed. The sample preparation method comprises the following steps: (1) The sample is ground uniformly by an agate mortar, then dispersed in ethanol solution and treated by ultrasonic waves in an ultrasonic instrument for half an hour, finally, a proper amount of suspension liquid is dripped on an ultrathin carbon support film copper mesh by a dropper, and the test can be carried out after natural drying at room temperature.
The phenol conversion test step in FIG. 2: after the completion of the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected and analyzed by gas chromatography under the conditions shown in Table 1. In the cyclic reaction, each catalytic reaction was carried out under the same reaction conditions (reaction conditions: 6mL of methanol, 1.000g of phenol, mass ratio of catalyst to phenol used was 1:10, phenol/H 2 O 2 The molar ratio is 3:1, the reaction temperature is 60 ℃, and the reaction time is 6 h). After each reaction, the catalyst was collected from the reaction mixture, washed with methanol solution, and dried in an oven at 100 ℃ overnight for the next reaction.
In the present invention, the ultrasonic treatment is carried out for 1 second and stopped for 5 seconds, which is an ultrasonic cycle.
Example 1:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (2) was 3:1, and stirring was continued for 6 hours at normal pressure. When the reaction temperature is raised to 60 DEG CImmediately adding ultrasonic operation, wherein the ultrasonic power density is 5W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 2:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 3:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 10KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 4:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When (when)Immediately adding ultrasonic operation when the reaction temperature is raised to 60 ℃, wherein the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 3, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 5:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 3, the treatment time is 30min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 6:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 30min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
example 7:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1 at ordinary timesStirring was continued for 6h under pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 40min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
comparative example 1:
a method for hydroxylating phenol of a TS-1 titanium silicalite molecular sieve, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
comparative example 2:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 20W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 40min, and the ultrasonic probe is arranged at the middle position of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
comparative example 3:
an ultrasonic-assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method, comprising the steps of:
the phenol hydroxylation reaction was carried out with stirring in a 50mL three-necked flask reactor. Firstly, 1.000g of phenol is dissolved in 6mL of methanol, then a certain amount of TS-1 titanium silicalite molecular sieve catalyst is added, and the mass ratio of the added catalyst to the mass of the phenol is 1:10. the reaction temperature was slowly increased to 60 ℃ with stirring. Then, H is 2 O 2 (30 wt%) of phenol and H were gradually added to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring was continued for 6h at normal pressure. When the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 50KHz, and the interval ratio is 1:3, the treatment time is 40min, and the treatment is superbThe acoustic probe is placed in the middle of the liquid. After the reaction, the catalyst was centrifuged from the reaction mixture, and the supernatant was collected for gas chromatography. The results of the gas chromatography analysis are as follows:
examples 1 to 7 are experiments after adding ultrasound during the reaction, comparative example 1 is an experiment of normal reaction without adding ultrasound, and comparative examples 2 to 3 are ultrasonic experiments beyond the ultrasonic conditions of the present invention. Example 1 was selected for TGA (Thermogravimetric Analysis) thermogravimetric analysis with comparative example 1 and cycle 5, 10 and 15 results were taken for comparison respectively:
as seen from the transmission electron micrograph of FIG. 1, the ultrasonic operation at the intensity of examples 1 to 7 did not destroy the molecular sieve framework structure, whereas FIG. 2 shows that comparative examples 2 to 3 exhibited TS-1 molecular sieve crushing after both the ultrasonic power density and the ultrasonic frequency were outside the scope of the ultrasonic conditions of the present invention.
As can be seen from the gas chromatography analysis of the phenol hydroxylation reaction, in the first catalytic reaction, the phenol conversion in examples 1 to 7 to which ultrasound was added was significantly higher than that in comparative example 1 to which no ultrasound was added. In the subsequent cyclic reaction, the phenol conversion rate decreases more slowly with the number of cycles than in the conventional reaction process. The phenol conversion in example 1 with added ultrasound was kept around 63% of the first reaction phenol conversion while the phenol conversion in comparative example 1 without added ultrasound was only around 18% of the first reaction phenol conversion when recycled to 15 times. It can be seen that the deactivation rate of the catalyst after addition of ultrasound is significantly slowed.
Comparative example 2 is an increase in ultrasonic power density based on example 7, and comparative example 3 is an increase in ultrasonic frequency based on example 7. As can be seen from the gas chromatographic analysis, the conversion rate of the integral phenol hydroxylation was rapidly reduced from about 26% of the previous 5 times to 17% (comparative example 2) and 15% (comparative example 3).
R5, R10 and R15 in FIG. 3 represent TS-1 catalysts obtained by centrifugation from the reaction system after 5 cycles, 10 cycles and 15 cycles, respectively. The main products of the reaction include catechol, hydroquinone and benzoquinone, but with the increase of the cycle times, carbon deposition phenomenon may occur, and the condensation of the catechol, benzoquinone and the like generates viscous substances such as phenol tar and the like. The main products catechol, hydroquinone and benzoquinone have boiling points of 245 ℃, 286 ℃ and 293 ℃, respectively, so that substances decomposed at a temperature higher than 245 ℃ should be catechol, hydroquinone, benzoquinone, tar and the like. The thermal gravimetric analysis of the molecular sieves revealed that the weight loss rates of R5-ultrasonic and R5-conventional were (4.1%) and (14.6%) respectively, the weight loss rates of R10-ultrasonic and R10-conventional were (4.8%) and (16.3%) respectively, the weight loss rates of R15-ultrasonic and R15-conventional were (6.8%) and (18.3%) respectively, and the weight loss rates of R5-ultrasonic, R10-ultrasonic and R15-ultrasonic were lower than those of the corresponding conventional TS-1 catalysts, indicating that the addition of ultrasonic during the reaction slowed down the adsorption of the product and by-products in the catalyst channels, thereby reducing the coverage of the active sites and the blockage of the molecular sieves, and slowing down the deactivation rate.
The above analysis shows that the addition of ultrasonic operation can effectively prolong the service life of the molecular sieve catalyst, but the setting of ultrasonic operation is extremely critical through comparative examples 2-3, the ultrasonic power density is 5-8W/mL, the frequency is 10-20 KHz, the ultrasonic power density is 5-8W/mL, and the frequency is 10-20 KHz, thus the ultrasonic power density and the frequency can be synergistically increased. According to the invention, through a great deal of experimental exploration in the early stage, the ultrasonic operation conditions suitable for the TS-1 molecular sieve are gradually determined by analyzing the synergistic effect of different operation conditions, and the service life of the TS-1 titanium silicalite molecular sieve is finally prolonged in multiple times.
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (6)
1. An ultrasonic assisted TS-1 titanium silicalite molecular sieve phenol hydroxylation method is characterized in that: the method comprises the following steps:
phenol hydroxylation reaction is carried out under stirring conditions, phenol is firstly dissolved in methanol, then TS-1 titanium silicalite molecular sieve catalyst is added, and the reaction temperature is slowly increased to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 The solution was gradually added to the reaction mixture, phenol and H 2 O 2 The molar ratio of (2) is 3:1, stirring is continued for 6 hours under normal pressure, when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 5-8W/mL, the frequency is 10-20 KHz, and the interval ratio is 1: 3-1: and 5, the treatment time is 10-40 min, and the ultrasonic probe is arranged at the middle position of the liquid.
2. The method according to claim 1, characterized in that: the conditions of the ultrasound are: the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 20min, and the ultrasonic probe is arranged at the middle position of the liquid.
3. The method according to claim 1, characterized in that: the mass ratio of the TS-1 titanium silicalite molecular sieve catalyst to the phenol is 1:10 to 1:15.
4. the method according to claim 1, characterized in that: the method comprises the following steps:
phenol hydroxylation is carried out under stirring conditions by first dissolving phenol in methanol, phenol: ratio of methanol g: mL is 1: and 6, adding a TS-1 titanium silicalite molecular sieve catalyst, wherein the mass ratio of the added catalyst to the mass of phenol is 1:10. slowly increasing the reaction temperature to 60 ℃ under stirring; then, H with a mass concentration of 30wt% 2 O 2 Gradually adding phenol and H to the reaction mixture 2 O 2 The molar ratio of (3): 1, stirring continuously for 6 hours under normal pressure;when the reaction temperature is raised to 60 ℃, ultrasonic operation is immediately added, the ultrasonic power density is 8W/mL, the frequency is 20KHz, and the interval ratio is 1: and 5, the treatment time is 40min, and the ultrasonic probe is arranged at the middle position of the liquid.
5. The method according to any one of claims 1 to 4, wherein: the sonication was for 1 second and stopped for 5 seconds, which is one sonication cycle.
6. Use of the method according to any one of claims 1 to 5 for extending the lifetime of a TS-1 titanium silicalite molecular sieve.
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