CN112591762A - Ultrasonic-assisted titanium-silicon molecular sieve modification method - Google Patents

Ultrasonic-assisted titanium-silicon molecular sieve modification method Download PDF

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CN112591762A
CN112591762A CN202011475741.7A CN202011475741A CN112591762A CN 112591762 A CN112591762 A CN 112591762A CN 202011475741 A CN202011475741 A CN 202011475741A CN 112591762 A CN112591762 A CN 112591762A
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titanium
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刘绚艳
佘媛媛
刘军
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Hunan Vocational College of Chemical Technology
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Abstract

The invention discloses an ultrasonic-assisted titanium silicalite molecular sieve modification method, which relates to the technical field of molecular sieve modification, and comprises the following steps: s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol at one time, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of (33-42) to (5.5-14.8) to 1; s2, heating to remove alcohol, heating the mixed solution for the second time to remove alcohol to obtain titanium-silicon gel-forming reaction solution, heating the titanium-silicon gel-forming reaction solution to crystallize at the temperature of 170-195 ℃, wherein the crystallization time is 55-65h, performing solid-liquid separation on the obtained solid-liquid mixture to obtain raw powder mother solution and solid, washing, drying and roasting the solid, performing superfine grinding treatment on the roasted solid, and filtering by a sieve of 80 meshes to obtain raw powder of the titanium-silicon molecular sieve; the invention is beneficial to the combination of metal salt and the titanium silicalite molecular sieve, and further improves the catalytic oxidation activity.

Description

Ultrasonic-assisted titanium-silicon molecular sieve modification method
Technical Field
The invention relates to the technical field of molecular sieve modification, in particular to an ultrasonic-assisted titanium silicalite molecular sieve modification method.
Background
The titanium-silicon molecular sieve is prepared from Ti4+Partial Si substituted all-silicon molecular sieve4+A zeolite molecular sieve with MFI type structure is formed. Due to the ion Ti4+Has the characteristic of six coordination and has the potential of accepting electron pairs, so that the molecular sieve has the potential of H2O2Or the organic peroxide compound has good adsorption activation performance.
Cyclohexanone oxime is considered as an important chemical production raw material, and is a key intermediate for producing nylon-6 monomer epsilon-caprolactam. The successful development of cyclohexanone ammoximation process from cyclohexanone, ammonia and H in Montedipes.p.A.in Italy in the 80 th century2O2The cyclohexanone ammoximation reaction is carried out on the raw material under the catalytic action of the titanium silicalite molecular sieve to prepare the cyclohexanone oxime. The production process is simple, mild in condition, environment-friendly, high in reactant conversion rate and product selectivity, and capable of greatly improving industrial benefit, so that the development of the process is of great significance to the industrial production of caprolactam. The titanium-silicon molecular sieve is also applied to other organic oxidation reactions and has wide application potential.
However, the existing titanium silicalite molecular sieve has large grain size and large pore volume size, which is not beneficial to actual catalysis, and meanwhile, the metal compound is not easy to be grafted in the pore volume of the titanium silicalite molecular sieve.
Therefore, an ultrasonic-assisted titanium silicalite molecular sieve modification method is provided to solve the problems.
Disclosure of Invention
The invention aims to provide an ultrasonic-assisted titanium silicalite molecular sieve modification method to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: an ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol at one time, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of (33-42) to (5.5-14.8) to 1;
s2, heating to remove alcohol, heating the mixed solution for the second time to remove alcohol to obtain titanium-silicon gel-forming reaction solution, heating the titanium-silicon gel-forming reaction solution to crystallize at the temperature of 170-195 ℃, wherein the crystallization time is 55-65h, performing solid-liquid separation on the obtained solid-liquid mixture to obtain raw powder mother solution and solid, washing, drying and roasting the solid, performing superfine grinding treatment on the roasted solid, and filtering by a sieve of 80 meshes to obtain raw powder of the titanium-silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 30-80 ℃ and the mixing time at 3.5-4.25h to obtain the titanium-silicon molecular sieve with the mass ratio: metal salt: acid 0.01: (0.005-5): (0.001-3);
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, and crystallizing the substances in the crystallization kettle for 3-72 hours after the ultrasonic treatment is finished, wherein the temperature in the crystallization kettle is controlled at 80-170 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 65-83 deg.C, drying the washed substance in a drying oven at 125-180 deg.C for 1-15h, purging dry nitrogen gas in the drying oven during drying, and controlling the purging dry nitrogen gas speed at 20-30m3/min；
S6: and roasting to obtain the modified titanium silicalite molecular sieve.
Furthermore, the temperature of the primary heating and alcohol removal in the step S1 is 78-86 ℃, and the alcohol removal time is 2.8-5.2 h.
Furthermore, the temperature of the secondary heating for removing the alcohol in the step S2 is 83-95 ℃, and the time for removing the alcohol is 4.5-5.3 h.
Furthermore, the acid in the step S3 is selected from inorganic acid, the pH of the inorganic acid is 5.5-6.3, and the concentration of the inorganic acid is 1.1-1.4 mol/L.
Further, the inorganic acid is hydrofluoric acid.
Furthermore, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 3.5-5.2 nm.
Furthermore, the power of the ultrasonic instrument is controlled to be 180-230W, and the ultrasonic treatment time is 1.5-2.2 h.
Furthermore, the roasting temperature of the step S5 is 350-600 ℃, and the roasting time is 2-15 h.
Furthermore, the size of the loaded crystal grain of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 6-8 nm.
The invention has the beneficial effects that:
the silicon molecular sieve raw powder mother liquor, the template agent, the mesoporous silica and the tetrabutyl titanate are mixed, then the mixture is heated twice to remove alcohol, and then crystallization, washing, drying, roasting and superfine grinding treatment are carried out to realize the primary modification of the titanium silicon molecular sieve raw powder, thus being beneficial to reducing the grain size of the titanium silicon molecular sieve raw powder, improving the pore volume of the titanium silicon molecular sieve raw powder, improving the specific surface area, being beneficial to the surface utilization rate of the titanium silicon molecular sieve raw powder and being beneficial to improving the catalytic oxidation activity; then carrying out mixed reaction on the titanium silicalite molecular sieve, metal salt and an acid solution, and then carrying out crystallization, washing, drying under dry nitrogen and roasting treatment, so that the metal salt can be embedded into the pore volume of the titanium silicalite molecular sieve, the combination of the metal salt and the titanium silicalite molecular sieve can be facilitated, and the catalytic oxidation activity can be further improved; through experimental data analysis, the cyclohexanone conversion rate, the catalytic life, the particle size, the pore volume and the specific surface are obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further described with reference to the following examples.
Example 1
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 78 ℃, the time for removing alcohol is 2.8 hours, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate with the molar ratio of 42:14.8: 1;
s2, heating to remove alcohol, heating the mixed solution twice to remove alcohol, wherein the temperature for heating and removing alcohol for the second time is 83 ℃ and the time for removing alcohol is 4.5 hours, thus obtaining titanium silicon gel-forming reaction liquid, heating and crystallizing the titanium silicon gel-forming reaction liquid, the temperature for heating and crystallizing is 170 ℃, the time for crystallizing is 65 hours, carrying out solid-liquid separation on the obtained solid-liquid mixture, thus obtaining raw powder mother liquor and solid, washing, drying and roasting the solid, carrying out superfine grinding treatment on the solid after roasting, and filtering with a sieve of 80 meshes to obtain raw powder of the titanium silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 80 ℃ and the mixing time at 3.8h to obtain the titanium-silicon molecular sieve with the mass ratio of: metal salt: acid 0.01: 5: 0.001, wherein the acid is inorganic acid, the pH value of the inorganic acid is 6.3, the concentration of the inorganic acid is 1.1mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 5.2 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 180W, controlling the ultrasonic treatment time to be 1.5h, crystallizing substances in the crystallization kettle for 72h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 170 ℃;
s5: then go toWashing crystallized substances with deionized water at constant temperature, controlling the washing temperature to 83 deg.C, drying the washed substances in a drying oven at 125 deg.C for 12h, purging dry nitrogen gas in the drying oven at 30m3/min；
S6: and roasting at the roasting temperature of 350 ℃ for 15h to obtain the modified titanium silicalite molecular sieve, wherein the load grain size of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 6 nm.
Example 2
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 86 ℃, the time for removing alcohol is 3.3 hours, and then adding tetrabutyl titanate, the template agent, the mesoporous silica and the tetrabutyl titanate with the molar ratio of 33:5.5: 1;
s2, heating to remove alcohol, heating the mixed solution for the second time to remove alcohol at 95 ℃ for 4.8h to obtain titanium-silicon gel-forming reaction solution, heating the titanium-silicon gel-forming reaction solution for crystallization at 195 ℃ for 55h, separating solid from liquid to obtain raw powder mother solution and solid, washing, drying and roasting the solid, superfine grinding the solid, and filtering with a 80-mesh sieve to obtain raw powder of the titanium-silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 70 ℃ and the mixing time at 4.25h to obtain the titanium-silicon molecular sieve with the mass ratio of: metal salt: acid 0.01: 1.3: 3, the acid is inorganic acid, the pH of the inorganic acid is 5.5, the concentration of the inorganic acid is 1.2mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 3.5 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 230W, controlling the ultrasonic treatment time to be 1.8h, crystallizing the substance in the crystallization kettle for 3h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 80 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 65 deg.C, drying the washed substance in a drying oven at 140 deg.C for 9h, purging dry nitrogen gas in the drying oven at 29m3/min；
S6: and roasting at the roasting temperature of 600 ℃ for 2h to obtain the modified titanium silicalite molecular sieve, wherein the load grain size of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 7 nm.
Example 3
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 79 ℃, the time for removing alcohol is 3.8 hours, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate with the molar ratio of 36:9.8: 1;
s2, heating to remove alcohol, performing secondary heating to remove alcohol on the mixed solution, wherein the temperature for secondary heating to remove alcohol is 87 ℃, and the time for removing alcohol is 5.3 hours, so as to obtain titanium-silicon colloid-forming reaction liquid, heating to crystallize the titanium-silicon colloid-forming reaction liquid, wherein the temperature for heating to crystallize is 178 ℃, and the time for crystallizing is 58 hours, performing solid-liquid separation on the obtained solid-liquid mixture, so as to obtain raw powder mother liquor and solid, washing, drying and roasting the solid, performing superfine grinding treatment on the solid after roasting, and filtering by a sieve of 80 meshes, so as to obtain raw powder of the titanium-silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 50 ℃ and the mixing time at 3.7h to obtain the titanium-silicon molecular sieve with the mass ratio: metal salt: acid 0.01: 0.005: 0.8, wherein the acid is inorganic acid, the pH value of the inorganic acid is 5.8, the concentration of the inorganic acid is 1.4mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 3.9 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 190W, controlling the ultrasonic treatment time to be 2.1h, crystallizing substances in the crystallization kettle for 56h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 120 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 69 deg.C, drying the washed substance in a drying oven at 180 deg.C for 1h, purging dry nitrogen gas in the drying oven at 23m3/min；
S6: roasting at the roasting temperature of 420 ℃ for 5h to obtain the modified titanium silicalite molecular sieve, wherein the load grain size of the modified titanium silicalite molecular sieve is 16nm, and the pore diameter of the modified titanium silicalite molecular sieve is 8 nm.
Example 4
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 81 ℃, the time for removing alcohol is 4.4 hours, and then adding tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of 39:11.2: 1;
s2, heating to remove alcohol, heating the mixed solution twice to remove alcohol, wherein the temperature for heating and removing alcohol for the second time is 89 ℃, and the time for removing alcohol is 5.1h, thus obtaining titanium silicon gel-forming reaction liquid, heating and crystallizing the titanium silicon gel-forming reaction liquid, wherein the temperature for heating and crystallizing is 185 ℃, and the time for crystallizing is 62h, carrying out solid-liquid separation on the obtained solid-liquid mixture, thus obtaining raw powder mother liquor and solid, washing, drying and roasting the solid, carrying out superfine grinding treatment on the solid after roasting, and filtering by a sieve of 80 meshes, thus obtaining raw powder of the titanium silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 30 ℃ and the mixing time at 3.9h to obtain the titanium-silicon molecular sieve with the mass ratio: metal salt: acid 0.01: 2.3: 1.4, the acid is inorganic acid, the pH value of the inorganic acid is 6.1, the concentration of the inorganic acid is 1.4mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 4.2 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 210W, controlling the ultrasonic treatment time to be 1.9h, crystallizing the substance in the crystallization kettle for 48h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 150 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 72 deg.C, drying the washed substance in a drying oven at 165 deg.C for 15h, purging dry nitrogen gas in the drying oven at 23m3/min；
S6: and roasting at 490 ℃ for 8h to obtain the modified titanium silicalite molecular sieve, wherein the size of the loaded crystal grain of the modified titanium silicalite molecular sieve is 16nm, and the pore diameter of the modified titanium silicalite molecular sieve is 8 nm.
Example 5
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 83 ℃, the time for removing alcohol is 5.2 hours, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of 41:7.3: 1;
s2, heating to remove alcohol, heating the mixed solution for the second time to remove alcohol at 91 ℃ for 4.7 hours to obtain titanium-silicon gel-forming reaction solution, heating the titanium-silicon gel-forming reaction solution for crystallization at 180 ℃ for 60 hours, separating solid from liquid to obtain raw powder mother solution and solid, washing, drying and roasting the solid, superfine grinding the solid, and filtering with a 80-mesh sieve to obtain raw powder of the titanium-silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 40 ℃ and the mixing time at 4.1h to obtain the titanium-silicon molecular sieve with the mass ratio of: metal salt: acid 0.01: 3.5: 2.1, the acid is inorganic acid, the pH of the inorganic acid is 6, the concentration of the inorganic acid is 1.2mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 4.8 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 195W, controlling the ultrasonic treatment time to be 1.9h, crystallizing the substance in the crystallization kettle for 18h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 110 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 76 deg.C, drying the washed substance in a drying oven at 150 deg.C for 6h, purging dry nitrogen gas in the drying oven at a speed of 27m3/min；
S6: roasting at 550 ℃ for 11h to obtain the modified titanium silicalite molecular sieve, wherein the size of the load crystal grain of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 7 nm.
Comparative example 1
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of 42:14.8: 1;
s2, heating to remove the alcohol, and then carrying out secondary heating to remove the alcohol on the mixed solution to obtain titanium-silicon molecular sieve raw powder;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 80 ℃ and the mixing time at 3.8h to obtain the titanium-silicon molecular sieve with the mass ratio of: metal salt: acid 0.01: 5: 0.001, wherein the acid is inorganic acid, the pH value of the inorganic acid is 6.3, the concentration of the inorganic acid is 1.1mol/L, the inorganic acid is hydrofluoric acid, the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 5.2 nm;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 180W, controlling the ultrasonic treatment time to be 1.5h, crystallizing substances in the crystallization kettle for 72h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 170 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 83 deg.C, drying the washed substance in a drying oven at 125 deg.C for 12h, purging dry nitrogen gas in the drying oven at 30m3/min；
S6: and roasting at the roasting temperature of 350 ℃ for 15h to obtain the modified titanium silicalite molecular sieve, wherein the load grain size of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 6 nm.
Comparative example 2
An ultrasonic-assisted titanium silicalite molecular sieve modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol for one time, wherein the temperature for removing alcohol for one time is 78 ℃, the time for removing alcohol is 2.8 hours, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate with the molar ratio of 42:14.8: 1;
s2, heating to remove alcohol, heating the mixed solution twice to remove alcohol, wherein the temperature for heating and removing alcohol for the second time is 83 ℃ and the time for removing alcohol is 4.5 hours, thus obtaining titanium silicon gel-forming reaction liquid, heating and crystallizing the titanium silicon gel-forming reaction liquid, the temperature for heating and crystallizing is 170 ℃, the time for crystallizing is 65 hours, carrying out solid-liquid separation on the obtained solid-liquid mixture, thus obtaining raw powder mother liquor and solid, washing, drying and roasting the solid, carrying out superfine grinding treatment on the solid after roasting, and filtering with a sieve of 80 meshes to obtain raw powder of the titanium silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 80 ℃ and the mixing time at 3.8 h;
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, controlling the power of the ultrasonic instrument to be 180W, controlling the ultrasonic treatment time to be 1.5h, crystallizing substances in the crystallization kettle for 72h after the ultrasonic treatment is finished, and controlling the temperature in the crystallization kettle to be 170 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 83 deg.C, drying the washed substance in a drying oven at 125 deg.C for 12h, purging dry nitrogen gas in the drying oven at 30m3/min；
S6: and roasting at 350 ℃ for 15h to obtain the modified titanium-silicon molecular sieve.
Test example:
the product obtained in comparative example 1 was subjected to agilent 7890 chromatography to determine the conversion of cyclohexanone and the selectivity of cyclohexanone oxime.
The titanium silicalite molecular sieve modified in each example is used for cyclohexanone ammoximation reaction according to the method of comparative example 1 instead of unmodified TS-1 molecular sieve, the obtained product is used for measuring the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime by Agilent 7890 chromatography, and the specific results are shown in Table 1
Wherein the cyclohexanone conversion (amount of added cyclohexanone-amount of remaining cyclohexanone)/amount of added cyclohexanone × 100%
Cyclohexanone oxime selectivity is the amount of cyclohexanone consumed for conversion to cyclohexanone oxime/amount of cyclohexanone converted x 100%
Figure RE-GDA0002915235740000111
Through experimental data analysis, the cyclohexanone conversion rate, the catalytic life, the particle size, the pore volume and the specific surface are obviously improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (9)

1. An ultrasonic-assisted titanium silicalite molecular sieve modification method is characterized in that: the modification method comprises the following steps:
s1, mixing the silicon molecular sieve raw powder mother liquor, the template agent and the mesoporous silica according to the proportion, heating for removing alcohol at one time, and then adding the tetra-n-butyl titanate, the template agent, the mesoporous silica and the tetra-n-butyl titanate according to the molar ratio of (33-42) to (5.5-14.8) to 1;
s2, heating to remove alcohol, heating the mixed solution for the second time to remove alcohol to obtain titanium-silicon gel-forming reaction solution, heating the titanium-silicon gel-forming reaction solution to crystallize at the temperature of 170-195 ℃, wherein the crystallization time is 55-65h, performing solid-liquid separation on the obtained solid-liquid mixture to obtain raw powder mother solution and solid, washing, drying and roasting the solid, performing superfine grinding treatment on the roasted solid, and filtering by a sieve of 80 meshes to obtain raw powder of the titanium-silicon molecular sieve;
s3, adding the raw powder of the titanium-silicon molecular sieve obtained in the step S2 into a mixed water solution containing metal salt and acid solution, controlling the mixing temperature at 30-80 ℃ and the mixing time at 3.5-4.25h to obtain the titanium-silicon molecular sieve with the mass ratio: metal salt: acid 0.01: (0.005-5): (0.001-3);
s4: placing the mixture obtained in the step S3 in a crystallization kettle, placing the crystallization kettle in an ultrasonic instrument for ultrasonic treatment, and crystallizing substances in the crystallization kettle for 3-72 hours after the ultrasonic treatment is finished, wherein the temperature in the crystallization kettle is controlled at 80-170 ℃;
s5: then washing the crystallized substance with deionized water at constant temperature, controlling the washing temperature at 65-83 deg.C, drying the washed substance in a drying oven at 125-180 deg.C for 1-15h, purging dry nitrogen gas in the drying oven during drying, and controlling the purging dry nitrogen gas speed at 20-30m3/min；
S6: and roasting to obtain the modified titanium silicalite molecular sieve.
2. The method of claim 1, wherein the method comprises the following steps: the temperature of the primary heating and alcohol removing in the step S1 is 78-86 ℃, and the alcohol removing time is 2.8-5.2 h.
3. The method of claim 2, wherein the method comprises the following steps: the temperature of the secondary heating and alcohol removal in the step S2 is 83-95 ℃, and the alcohol removal time is 4.5-5.3 h.
4. The method of claim 3, wherein the method comprises the following steps: and the acid in the step S3 is inorganic acid, the pH of the inorganic acid is 5.5-6.3, and the concentration of the inorganic acid is 1.1-1.4 mol/L.
5. The method of claim 4, wherein the method comprises the following steps: the inorganic acid is hydrofluoric acid.
6. The method of claim 5, wherein the method comprises the following steps: the metal salt is tantalum pentoxide, niobium sulfide or niobium pentoxide, and the particle size of the metal salt is 3.5-5.2 nm.
7. The method of claim 1, wherein the method comprises the following steps: the power of the ultrasonic instrument is controlled to be 180-230W, and the ultrasonic treatment time is 1.5-2.2 h.
8. The method of claim 1, wherein the method comprises the following steps: the roasting temperature of the step S5 is 350-600 ℃, and the roasting time is 2-15 h.
9. The method of claim 8, wherein the method comprises the following steps: the size of the load crystal grain of the modified titanium silicalite molecular sieve is 16nm, and the aperture of the modified titanium silicalite molecular sieve is 6-8 nm.
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