CN115974094A - Titanium-silicon molecular sieve, and synthesis method and application thereof - Google Patents
Titanium-silicon molecular sieve, and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a titanium-silicon molecular sieve and a synthesis method and application thereof. Tetramethoxysilane is used as a silicon source, tetrabutyl titanate is used as a titanium source, tetrapropylammonium hydroxide is used as a template agent, ethanol and isopropanol are used as solvents, and a hydrothermal method is adopted to synthesize the titanium-silicon molecular sieve. According to the invention, tetramethoxysilane is used for replacing tetraethoxysilane in the traditional hydrothermal method, and the catalytic performance of the titanium-silicon molecular sieve synthesized by taking tetraethoxysilane as a raw material can be still achieved. However, the market price of the tetramethoxysilane is far lower than that of the tetraethoxysilane, so that the production cost of the titanium-silicon molecular sieve is remarkably reduced, and the synthesis of the titanium-silicon molecular sieve by using the tetramethoxysilane as the raw material has the industrial significance of large-scale production.
Description
Technical Field
The invention belongs to the field of molecular sieve material preparation, and relates to a method for synthesizing a titanium-silicon molecular sieve by using tetramethoxysilane as a raw material and application of the titanium-silicon molecular sieve in allyl chloride epoxidation.
Background
The titanium silicalite TS-1 belongs to an orthorhombic system and has the same MFI topological structure as the ZSM-5 molecular sieve. Due to the introduction of the transition metal titanium, the TS-1 has unique catalytic oxidation performance. TS-1 is widely used in olefin epoxidation, hydroxylation of phenol and benzene, partial oxidation of alkane, alcohol oxidation, oximation of ketone and other catalytic oxidation reactions.
Titanium-silicon molecular sieves are usually synthesized by a hydrothermal method, and currently, synthesis systems are mainly divided into two types, one is a synthesis system taking tetraethoxysilane as a silicon source and tetrapropylammonium hydroxide as a template agent, and the other is a synthesis system taking silica sol as a silicon source and tetrapropylammonium bromide as a template agent. The former has high synthesis cost due to the high price of tetraethoxysilane and tetrapropylammonium hydroxide, while the latter has low cost but poor catalytic performance compared with the former. Therefore, the method has practical and industrial production significance on how to reduce the synthesis cost of the titanium silicalite molecular sieve under the condition of ensuring better catalytic performance.
Patent CN107500309B discloses a method for preparing a titanium-silicon molecular sieve, which uses ethyl orthosilicate as a silicon source and tetrabutyl titanate as a titanium source, wherein the molecular sieve is prepared by hydrolyzing, dealcoholizing, crystallizing, filtering, roasting, modifying and the like the silicon source and the titanium source, and the final catalyst is used for preparing cyclohexanone oxime by twice dealcoholizing, hydrolyzing the silicon source and then performing ammoxidation of hydrolyzed cyclohexanone of the titanium source.
Patent CN103641134B describes a preparation method of a titanium-silicon molecular sieve with controllable grain size, which comprises mixing tetraethoxysilane, tetrabutyl titanate, a template, an alkali source, an inorganic ammonium salt and a molecular sieve mother solution according to a molar ratio of SiO2: tiO2: template: alkali source: inorganic ammonium salt: H2O of 0.1-0.6.
Patent CN103214000B discloses a synthesis method of titanium-silicon molecular sieve TS-1, wherein a silicon source is subjected to acid-catalyzed hydrolysis, and then a titanium source is subjected to base-catalyzed hydrolysis at the same time, wherein the silicon source may be one or a mixture of more than two of methyl orthosilicate, ethyl orthosilicate and butyl orthosilicate. However, the specific process and application of the method for synthesizing titanium silicalite molecular sieve by using methyl orthosilicate as silicon source are not specifically described in the specific examples.
It can be seen that the synthesis of titanium-silicon molecular sieve using tetramethoxysilane as silicon source is not a conventional technical means, which may be due to the difference of hydrolysis rates between tetramethoxysilane and tetraethoxysilane, and the hydrolysis rate of the former is fast and is not easy to control. However, comparing the prices of the two, the price of tetramethoxysilane is only about one third of the price of tetraethoxysilane, and the same silicon content is obtained, and the usage amount of tetramethoxysilane is three quarters of the usage amount of tetraethoxysilane, so that the synthesis cost of the molecular sieve can be greatly reduced if tetramethoxysilane is used as the raw material to synthesize the titanium-silicon molecular sieve.
Disclosure of Invention
The invention provides a method for synthesizing a titanium-silicon molecular sieve by using tetramethoxysilane as a raw material, wherein the synthesized TS-1 has the same catalytic performance as the TS-1 synthesized by using tetraethoxysilane as a raw material, and the method obviously reduces the synthesis cost of the titanium-silicon molecular sieve and has industrial significance.
In order to achieve the purpose and the effect, the following scheme is adopted:
a process for synthesizing Ti-Si molecular sieve features that tetramethoxy silane as Si source, tetrabutyl titanate as Ti source, tetrapropyl ammonium hydroxide as template agent, and alcohol and isopropanol as solvent and hydrothermal method are used. The specific synthesis steps are as follows:
(1) Mixing tetramethoxysilane with ethanol, stirring and heating to 50-80 ℃, dropwise adding tetrabutyl titanate, keeping the temperature and stirring for 1-5 hours, and then cooling to 20-30 ℃.
(2) And (3) dropwise adding the aqueous solution of tetrapropylammonium hydroxide into the mixture in the step (1), controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 2-4 h after dropwise adding.
(3) And (3) mixing tetrabutyl titanate with isopropanol, dropwise adding the mixture into the mixture in the step (2), controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1-2 hours after dropwise adding.
(4) And (3) heating the mixture in the step (3), dealcoholizing and replenishing water, wherein the dealcoholizing temperature is 80-90 ℃, the dealcoholizing amount is 60-80% of the total feeding amount, and the water replenishing amount is 30-50% of the total feeding amount.
(5) And (3) putting the mixture in the step (4) into a stainless steel high-pressure reaction kettle, crystallizing at 160-180 ℃ for 48-120 h, cooling, filtering, washing, drying at 80-100 ℃, and roasting at 500-600 ℃ to obtain the titanium-silicon molecular sieve.
Further, according to the synthesis method, the mass ratio of the material charge amounts is tetramethoxysilane: ethanol: tetrabutyl titanate: isopropyl alcohol: tetrapropylammonium hydroxide: water =1, 0.6-1.5: 0.06-0.08.
Further, in the above synthesis method, the amount of tetrabutyl titanate added dropwise in step (1) is 0.1 to 1.5% by weight of tetramethoxysilane.
The invention provides a titanium silicalite molecular sieve synthesized by the method.
The invention provides application of the titanium silicalite molecular sieve in allyl chloride epoxidation reaction.
Further, in the above technical scheme, in the epoxidation reaction of allyl chloride, allyl chloride and H 2 O 2 The molar ratio is 2-5: 1, the mass ratio of methanol to hydrogen peroxide is 4-10: 1.
further, in the technical scheme, in the epoxidation reaction of the allyl chloride, the reaction temperature is 30-45 ℃, the reaction pressure is 0.2-1.0 MPa, and the mass space velocity of the allyl chloride is 0.5-5 h -1 。
The present invention will be further described with reference to the following specific examples.
Drawings
FIG. 1 is an XRD spectrum of a titanium silicalite C-1;
FIG. 2 is an SEM photograph of a titanium silicalite C-1;
FIG. 3 is an XRD spectrum of titanium silicalite D-1;
FIG. 4 is an SEM photograph of titanium silicalite D-1;
FIG. 5 is an SEM photograph of titanium silicalite D-2.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the scope of the invention.
The purity of the materials used in the examples was not less than 99%.
The synthesized titanium silicalite molecular sieve is used for allyl chloride epoxidation fixed bed reaction, inert quartz sand is added into two ends of a stainless steel jacketed reaction tube, 6g of titanium silicalite molecular sieve (20-40 meshes) is filled in the middle, the temperature of the reactor is kept by utilizing a super constant temperature water bath, reactants such as hydrogen peroxide, allyl chloride and solvent methanol are simultaneously fed, product analysis is carried out at regular time, and the reaction index is H 2 O 2 Conversion (X) H2O2 ) And epoxidation product selectivity (S) ECH ). The calculation method of the reaction index is as follows:
H 2 O 2 conversion X = reacted H 2 O 2 Mole number/H 2 O 2 Total moles 100%;
epichlorohydrin selectivity S ECH = moles of epichlorohydrin formed by reaction/moles of H reacted 2 O 2 Mole 100%.
The XRD characterization of the catalyst was determined by X-ray diffraction analyzer (Pasnake, X' Pert3 Powder).
Catalyst Scanning Electron Microscopy (SEM) characterization was measured by scanning electron microscopy (hitachi, SU 5000).
Example 1
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 60 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after the dropwise adding is finished. And mixing 32.5g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, with dealcoholizing amount of 1350g, and supplementing 897g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as C-1.
The XRD spectrogram and SEM picture of the titanium silicalite molecular sieve C-1 are shown in figure 1 and figure 2.
Example 2
Mixing 500g of tetramethoxysilane and 302g of ethanol, stirring and heating to 60 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and then cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after the dropwise adding is finished. Mixing 32.5g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, dealcoholizing amount of 1202g, and supplementing 900g of water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as C-2.
Example 3
Mixing 500g of tetramethoxysilane with 605g of ethanol, stirring and heating to 60 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after dropwise adding. And mixing 32.5g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, dealcoholizing amount of 1500g, and adding 895g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing at 170 ℃ for 96 hours, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting at 500 ℃ for 6 hours to obtain the titanium-silicon molecular sieve, which is marked as C-3.
Example 4
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 60 ℃, dropwise adding 1g of tetrabutyl titanate, keeping the temperature and stirring for 5 hours, and then cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after the dropwise adding is finished. And (3) mixing 34g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after the dropwise adding is finished. Heating, dealcoholizing at 80-90 deg.c in the amount of 1350g and replenishing water in 897g. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as C-4.
Example 5
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 60 ℃, dropwise adding 5g of tetrabutyl titanate, keeping the temperature and stirring for 1 hour, and then cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after the dropwise adding is finished. And (3) mixing 30g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1h after the dropwise adding is finished. Heating, dealcoholizing at 80-90 deg.C, with dealcoholizing amount of 1350g, and supplementing 897g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing at 170 ℃ for 96 hours, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting at 500 ℃ for 6 hours to obtain the titanium-silicon molecular sieve, which is marked as C-5.
Example 6
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 80 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and then cooling to 30 ℃. And (3) dropwise adding 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18%, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after dropwise adding. Mixing 32.5g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, with dealcoholizing amount of 1350g, and supplementing 897g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as C-6.
Example 7
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 60 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and then cooling to 30 ℃. 925g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 19 percent is dripped, the temperature in the kettle is controlled to be lower than 40 ℃, and the mixture is stirred for 3 hours after the dripping is finished. Mixing 37.5g of tetrabutyl titanate with 300g of isopropanol, dropwise adding the mixed material into a kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1h after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, dealcoholizing amount of 1400g, and supplementing 947g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing at 170 ℃ for 96 hours, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting at 500 ℃ for 6 hours to obtain the titanium-silicon molecular sieve, which is marked as C-7.
Example 8
Mixing 500g of tetramethoxysilane and 453g of ethanol, stirring and heating to 60 ℃, dropwise adding 2.5g of tetrabutyl titanate, keeping the temperature and stirring for 3 hours, and then cooling to 30 ℃. 610g of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 18% is dripped, the temperature in the kettle is controlled to be lower than 40 ℃, and the mixture is stirred for 3 hours after the dripping is finished. 27.5g of tetrabutyl titanate and 200g of isopropanol are mixed, the mixed materials are dripped into a kettle, the temperature in the kettle is controlled to be lower than 40 ℃, and the materials are stirred for 1 hour after the dripping is finished. Heating, dealcoholizing at 80-90 deg.C, dealcoholizing amount of 1300g, and supplementing 847g of water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as C-8.
Comparative example 1
684g of tetraethoxysilane is put into a kettle, 750g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 18 percent is dripped at 30 ℃, the temperature in the kettle is controlled to be lower than 40 ℃, and the stirring is carried out for 3 hours after the dripping is finished. And mixing 35g of tetrabutyl titanate with 250g of isopropanol, dropwise adding the mixed material into the kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1h after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, dealcoholizing amount of 900g, and replenishing water of 900g. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as D-1.
The XRD spectrogram and SEM picture of the titanium silicalite molecular sieve D-1 are shown in figure 3 and figure 4.
Comparative example 2
And (2) putting 500g of tetramethoxysilane into a kettle, dripping 750g of 18 mass percent tetrapropylammonium hydroxide aqueous solution at the temperature of 30 ℃, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 3 hours after dripping is finished. Mixing 35g of tetrabutyl titanate and 250g of isopropanol, dropwise adding the mixed materials into a kettle, controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1 hour after dropwise adding. Heating, dealcoholizing at 80-90 deg.C, with dealcoholizing amount of 1350g, and supplementing 897g water. And (3) putting the obtained material into a stainless steel high-pressure reaction kettle, crystallizing for 96 hours at 170 ℃, cooling, filtering, washing to be neutral, drying at 100 ℃, and roasting for 6 hours at 500 ℃ to obtain the titanium-silicon molecular sieve, which is marked as D-2.
The SEM photograph of the titanium silicalite D-2 is shown in figure 5.
Application example
The catalyst samples obtained in comparative example and example were evaluated for epoxidation performance of allyl chloride. Epoxidation is carried out in a fixed bed reactor, 6g (20-40 meshes) of catalyst is filled in the middle section of a stainless steel jacketed reaction tube, the upper end and the lower end of the reaction tube are filled with inert quartz sand, the reaction pressure is 0.5MPa, the reaction temperature is maintained to be 40 ℃ in a thermostatic water bath, raw materials of allyl chloride, hydrogen peroxide and solvent methanol are simultaneously fed, and the airspeed of the allyl chloride is 2h -1 Allyl chloride with H 2 O 2 The molar ratio is 3, the mass ratio of methanol to hydrogen peroxide is 8, the reaction is carried out for 24h, then sampling analysis is carried out, and the reaction results are shown in Table 1.
The results of evaluating the properties of the samples obtained in the comparative examples and examples are shown in Table 1.
As can be seen from the following table, the catalytic performance of the titanium silicalite molecular sieve synthesized by using tetramethoxysilane as the raw material can reach the catalytic performance of the titanium silicalite molecular sieve synthesized by using tetraethoxysilane as the raw material.
TABLE 1 evaluation results of catalytic Performance of each sample catalyst
| Serial number | Catalyst and process for producing the same | X H2O2 (％) | S ECH (％) |
| Example 1 | C-1 | 99.4 | 99.5 |
| Example 2 | C-2 | 99.6 | 99.0 |
| Example 3 | C-3 | 99.4 | 99.4 |
| Example 4 | C-4 | 99.5 | 99.3 |
| Example 5 | C-5 | 99.1 | 98.8 |
| Example 6 | C-6 | 99.2 | 99.2 |
| Example 7 | C-7 | 99.5 | 99.2 |
| Example 8 | C-8 | 99.0 | 99.4 |
| Comparative example 1 | D-1 | 99.5 | 99.3 |
| Comparative example 2 | D-2 | 97.5 | 97.3 |
Claims (7)
1. A method for synthesizing a titanium-silicon molecular sieve is characterized in that tetramethoxysilane is used as a silicon source, tetrabutyl titanate is used as a titanium source, tetrapropylammonium hydroxide is used as a template agent, ethanol and isopropanol are used as solvents, and the titanium-silicon molecular sieve is synthesized by a hydrothermal method, and the method comprises the following specific synthesis steps:
(1) Mixing tetramethoxysilane and ethanol, stirring and heating to 50-80 ℃, dropwise adding tetrabutyl titanate, keeping the temperature and stirring for 1-5 hours, and then cooling to 20-30 ℃;
(2) Dropwise adding the aqueous solution of tetrapropylammonium hydroxide into the mixture in the step (1), controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 2-4 hours after dropwise adding;
(3) Mixing tetrabutyl titanate and isopropanol, then dropwise adding the mixture into the mixture in the step (2), controlling the temperature in the kettle to be lower than 40 ℃, and stirring for 1-2 hours after dropwise adding;
(4) Heating the mixture in the step (3) to remove alcohol and supplement water, wherein the dealcoholization temperature is 80-90 ℃, the dealcoholization amount is 60-80% of the total feeding amount, and the water supplement amount is 30-50% of the total feeding amount;
(5) And (3) putting the mixture in the step (4) into a stainless steel high-pressure reaction kettle, crystallizing at 160-180 ℃ for 48-120 h, cooling, filtering, washing, drying at 80-100 ℃, and roasting at 500-600 ℃ to obtain the titanium-silicon molecular sieve.
2. The synthesis method according to claim 1, wherein the mass ratio of the material charge amounts is tetramethoxysilane: ethanol: tetrabutyl titanate: isopropyl alcohol: tetrapropylammonium hydroxide: water =1, 0.6-1.5: 0.06 to 0.08.
3. The synthesis method according to claim 1, wherein the tetrabutyl titanate is added dropwise in the step (1) in an amount of 0.1 to 1.5% by weight based on the weight of tetramethoxysilane.
4. A titanium silicalite molecular sieve synthesized according to the method of any one of claims 1 to 3.
5. Use of the titanium silicalite molecular sieve of claim 4 in an allyl chloride epoxidation reaction.
6. Use according to claim 5, characterized in that allyl chloride is reacted with H in an allyl chloride epoxidation reaction 2 O 2 The molar ratio is 2-5: 1, the mass ratio of methanol to hydrogen peroxide is 4-10: 1.
7. the method as claimed in claim 6, wherein the reaction temperature is 30-45 ℃, the reaction pressure is 0.2-1.0 MPa, and the mass space velocity of allyl chloride is 0.5-5 h -1 。
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