CN111057226A - Nano-load titanium-series composite catalyst, preparation method thereof and application thereof in polyester synthesis - Google Patents
Nano-load titanium-series composite catalyst, preparation method thereof and application thereof in polyester synthesis Download PDFInfo
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- CN111057226A CN111057226A CN201911393821.5A CN201911393821A CN111057226A CN 111057226 A CN111057226 A CN 111057226A CN 201911393821 A CN201911393821 A CN 201911393821A CN 111057226 A CN111057226 A CN 111057226A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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Abstract
The invention discloses a preparation method of a nano-loaded titanium composite catalyst, which comprises the steps of dissolving a titanium compound, tetraethoxysilane and a hydrolytic agent in absolute ethyl alcohol, and stirring and reacting for a certain time at room temperature to obtain a mixed solution; adding one or more metal salts selected from chlorides, acetates or phosphates of Mg, Al, Mn, Co and Zn into the mixed solution, continuously stirring, and heating to volatilize excessive solvent to obtain gel; and carrying out supercritical drying on the gel in the presence of a supercritical medium to obtain the final nano-loaded titanium composite catalyst. The catalyst prepared by the invention has strong hydrolytic resistance, can be stored for a long time and has stable activity; the catalyst has high catalytic activity and good stability, can effectively improve the esterification and polycondensation reaction efficiency, has stable performance in the reaction process, and has stable product index; the catalyst does not contain heavy metal, so that the harm to the environment and human is reduced; the polyester prepared by the catalyst has good hue, small yellow index and stable performance.
Description
Technical Field
The invention relates to the field of polyester catalysts, in particular to a nano-loaded titanium-based composite catalyst, a preparation method thereof and application thereof in polyester synthesis.
Background
Polyesters, which are polymers obtained by polycondensation of polyhydric alcohols and polybasic acids, are generally referred to mainly as polyethylene terephthalate (PET), and conventionally include linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate. Because of its excellent clothing application and high strength, it is quickly the largest variety of synthetic fibers. Due to excellent comprehensive performance, the composite material can maintain excellent physical performance in a wider temperature range, has high impact strength, good friction resistance, good rigidity, large hardness, small hygroscopicity, good dimensional stability and excellent electrical performance, is stable to most of organic solvents and inorganic acids, can be widely applied as a non-fiber polymer material, and can be further expanded to the fields of various containers, packaging materials, films, engineering plastics and the like.
The catalyst is of great importance in polyester production, the research on the catalyst is an important subject of the polyester industry, and scholars at home and abroad carry out extensive and deep research on the catalyst and the catalytic mechanism thereof in polyester production. At present, the polyester catalyst which is industrially produced and applied and researched more is mainly a compound of 3 series of antimony, germanium and titanium. The antimony catalyst has moderate activity and low price, so the antimony catalyst is commonly used in the polyester industry, but the antimony compound belongs to heavy metal, has the problems of being unfavorable to the health of human bodies, causing pollution to the environment and the like, and is gradually replaced by other catalysts; the germanium catalyst has good stability, side reactions are less in initiation in the reaction process, the prepared polyester has good color phase, but the catalytic activity is lower than that of an antimony system, the obtained polyester has more ether bonds, the melting point is lower, the germanium resource is rare, the price is high, the economic limit exists in the practical application, and the application is less; the titanium catalyst does not contain heavy metal, is safe and environment-friendly, has high catalytic activity and moderate price, and is expected to replace antimony catalysts in the future. At present, related research work on titanium catalysts is more, and partial products have good application in polyester, but the titanium catalysts are not short of defects, such as poor stability, easy hydrolysis, easy occurrence of more side reactions, uneven molecular weight distribution of products, yellow color of produced polyester products and the like, so that the application of the titanium catalysts is influenced. Therefore, the development of the efficient composite catalyst for producing the polyester has wide market prospect.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a nano-loaded titanium composite catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano-loaded titanium composite catalyst comprises the following steps:
dissolving a titanium compound, tetraethoxysilane and a hydrolytic agent in absolute ethyl alcohol, and stirring and reacting for a certain time at room temperature to obtain a mixed solution;
adding metal salt into the mixed solution, continuously stirring, heating to volatilize the redundant solvent to obtain gel; the metal salt is one or more of chlorides, acetates or phosphates of Mg, Al, Mn, Co and Zn;
and thirdly, performing supercritical drying on the gel in the presence of a supercritical medium to obtain the final nano-loaded titanium composite catalyst.
The technical principle of the application is as follows: according to the method, a nano titanium series compound polyester catalyst with higher activity and more stability is obtained by a sol-gel method, and other compound metal salts are added at the same time in a supercritical drying mode; specifically, in the first step, hydrolysis reaction of tetraethoxysilane is mainly carried out to generate nano silicon dioxide, and a titanium compound is attached to the nano silicon dioxide; compounding a titanium catalyst with chlorides, acetates or phosphates of Mg, Al, Mn, Co and Zn to improve the activity of the final catalyst; in combination with supercritical drying, the nanostructure of the catalyst material can be better maintained, thereby maintaining high catalyst activity.
As a preferred embodiment, in the step one, the reaction time is 1-4h (such as 1.2h, 1.5h, 2h, 2.5h, 3h, 3.5h and 3.8h)
In the preparation method of the nano-supported titanium composite catalyst, as a preferred embodiment, in the step one, the titanium compound is one or a mixture of more of n-butyl titanate, tetraethyl titanate, diisopropyl titanate, tetraisopropyl titanate, tetramethyl titanate and tetraoctyl titanate; the hydrolytic agent is water, or water and one or more selected from acetic acid, lactic acid, hydrochloric acid, phosphoric acid, malic acid and citric acid.
As a preferred embodiment, in the first step, the molar ratio of the titanium compound to the tetraethoxysilane is 1-30:1 (e.g., 3:1, 6:1, 10:1, 15:1, 20:1, 25:1, 28:1), preferably 5-20:1 (e.g., 6:1, 8:1, 10:1, 12:1, 15:1, 18: 1); the molar ratio of the titanium compound to the hydrolytic agent is 1:2-15 (such as 1:3, 1:5, 1:8, 1:10, 1:12, 1:14), preferably 1:5-10 (such as 1:6, 1:7, 1:8, 1: 9); the molar ratio of the titanium compound to the absolute ethyl alcohol is 1:2-20 (such as 1:4, 1:8, 1:12, 1:16, 1:18), preferably 1:5-10 (such as 1:6, 1:7, 1:8, 1: 9).
In a preferred embodiment of the method for preparing the nano-supported titanium composite catalyst, in the second step, after the metal salt is added, the mixture is stirred at room temperature for 1 to 2 hours (such as 1.2 hours, 1.5 hours and 1.8 hours), and then the mixture is heated to 40 to 100 ℃ (such as 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 95 ℃) and subjected to ultrasonic dispersion until the mixture becomes gel. The temperature rise and the ultrasonic dispersion are more favorable for volatilizing the redundant solvent and accelerating the formation of gel; too low a temperature will result in long preparation time, while too high a temperature will result in vigorous molecular motion and will not favor gel formation.
In the preparation method of the nano-supported titanium-based composite catalyst, as a preferred embodiment, in the step two, the molar ratio of the titanium-based compound to the metal cation of the compound metal salt is 20-1:1 (for example, 18:1, 15:1, 10:1, 8:1, 5:1, 3: 1); more preferably 10-3:1 (e.g. 9:1, 7:1, 6:1, 4: 1).
In the third step, the supercritical medium is carbon dioxide, methanol or ethanol; more preferably ethanol; the supercritical drying time is 0.5-2 hr (such as 0.8 hr, 1.0 hr, 1.2 hr, 1.5 hr, and 1.8 hr).
The main component of the nano-loaded titanium composite catalyst prepared by the method is nano-particles formed by loading nano-titanium dioxide and metal salt or metal oxide on nano-silicon dioxide; more preferably, the particle size of the nanoparticles is 10-500nm (such as 25nm, 50nm, 100nm, 200nm, 300nm, 400nm, 450nm, 480nm), and even more preferably 20-200nm (such as 30nm, 60nm, 90nm, 120nm, 150nm, 180 nm).
The invention also aims to provide the application of the nano-supported titanium composite catalyst in polyester synthesis.
Preferably, the catalyst is used in an amount of 5 to 100ppm (e.g., 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm), preferably 10 to 50ppm (e.g., 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm), calculated as the ratio of the titanium content in the catalyst to the mass of the finished polyester.
Compared with the prior art, the invention has the following beneficial effects:
the nano-loaded titanium composite catalyst prepared by the method has strong hydrolytic resistance, can be stored for a long time and has stable activity; the catalyst has high catalytic activity and good stability, can effectively improve the esterification and polycondensation reaction efficiency, has stable performance in the reaction process, and has stable product index; the catalyst does not contain heavy metal, so that the harm to the environment and human is reduced; the polyester prepared by the catalyst has good hue, small yellow index and stable performance.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
The starting materials used in the examples below are all commercial products.
Examples 1 to 6: synthesis of nano-loaded titanium series composite catalyst
Example 1
0.1mol of n-butyl titanate, 0.01mol of ethyl orthosilicate, 0.2mol of lactic acid and 0.3mol of water were dissolved in 100ml of absolute ethanol, and stirred and mixed at room temperature for 2 hours. 0.01mol of aluminum chloride and 0.01mol of cobalt acetate are added, stirring is continued for 1 hour at room temperature, and then heating is carried out to 50 ℃ and ultrasonic dispersion is carried out until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst A.
Example 2
0.1mol of tetraethyl titanate, 0.02mol of ethyl orthosilicate, 0.3mol of citric acid, and 0.3mol of water were dissolved in 100ml of anhydrous ethanol, and mixed with stirring at room temperature for 2.5 hours. Then 0.01mol of magnesium chloride and 0.02mol of cobalt acetate are added, the stirring is continued for 1 hour at room temperature, and then the mixture is heated to 40 ℃ and ultrasonically dispersed until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst B.
Example 3
A solution of 0.2mol of n-butyl titanate, 0.01mol of ethyl orthosilicate, 0.2mol of lactic acid and 0.3mol of water in 0.2mol of lactic acid was dissolved in 100ml of anhydrous ethanol and stirred and mixed at room temperature for 2 hours. Then 0.01mol of aluminum chloride and 0.01mol of zinc acetate are added, stirring is continued for 1 hour at room temperature, and then heating is carried out to 60 ℃ and ultrasonic dispersion is carried out until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst C.
Example 4
0.1mol of tetramethyl titanate, 0.02mol of ethyl orthosilicate, 0.3mol of hydrochloric acid and 0.3mol of water are dissolved in 100ml of absolute ethanol and mixed with stirring at room temperature for 2.5 hours. Then 0.01mol of zinc chloride and 0.01mol of cobalt acetate are added, the stirring is continued for 1 hour at room temperature, and then the mixture is heated to 50 ℃ and ultrasonically dispersed until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst D.
Example 5
0.2mol of n-butyl titanate, 0.015mol of ethyl orthosilicate, 0.2mol of citric acid and 0.3mol of water were dissolved in 100ml of absolute ethanol, and stirred and mixed at room temperature for 3 hours. Then 0.01mol of aluminum chloride, 0.01mol of zinc chloride and 0.01mol of cobalt acetate are added, the stirring is continued for 1 hour at room temperature, and then the mixture is heated to 60 ℃ and ultrasonically dispersed until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst E.
Example 6
0.15mol of n-butyl titanate, 0.02mol of ethyl orthosilicate, 0.2mol of acetic acid and 0.3mol of water are dissolved in 100ml of absolute ethanol and stirred and mixed for 2 hours at room temperature. Then 0.02mol of zinc chloride and 0.02mol of cobalt acetate are added, the stirring is continued for 1 hour at room temperature, and then the mixture is heated to 40 ℃ and ultrasonically dispersed until gel is formed. And adding the gel into an autoclave, using absolute ethyl alcohol as a supercritical medium, and performing supercritical drying on the gel for 60 minutes at the temperature of 262 ℃ and under the pressure of 8.5MPa to obtain the nano-loaded titanium composite catalyst F.
Examples 7 to 12: the PET polyester was synthesized using the nano-supported titanium-based composite catalysts prepared in examples 1 to 6.
Example 7
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst A, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Example 8
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst B, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Example 9
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst C, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Example 10
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst D, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Example 11
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst E, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Example 12
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst F, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Comparative example 1
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, stirring and mixing uniformly, then adding 10ppm (mass ratio of titanium to finished product) of titanium glycol, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
Comparative example 2
The comparative example synthesizes the nano-loaded titanium composite catalyst, compared with the example 5, the drying method is different, and the drying system of the comparative example adopts the steps of calcining and drying at 400 ℃ for 3 hours to finally prepare the nano-loaded titanium composite catalyst G.
Weighing 8.6kg of terephthalic acid and 4.2kg of ethylene glycol, uniformly stirring and mixing, adding 10ppm (mass ratio of titanium to finished product) of nano-loaded titanium composite catalyst G, introducing into a reaction kettle, and starting esterification reaction at the esterification temperature of 250 ℃ for 2.5 hours. After the esterification reaction, 1.25g of phosphoric acid is added, the mixture is vacuumized and decompressed until the system pressure is less than 100Pa, the polycondensation reaction is started, the polycondensation temperature is 275 ℃, the reaction time is 2 hours, and then the product is extruded, cooled and granulated through a casting belt opening, and the sample is taken for performance test.
The polyester products obtained in examples 7 to 12 above and the polyester products obtained in comparative examples 1 and 2 were sampled for intrinsic viscosity and color value tests, respectively, and the relevant parameters were measured by the following methods.
Intrinsic Viscosity (IV): the molecular weight of the polyester is determined according to GB/T14190-2008, the solvent is a mixed solvent of phenol and tetrachloroethane with 60/40 weight ratio, the testing temperature is 25 ℃, and the polymer concentration is 5 mg/mL.
Polyester color number: polyester chip color values were measured using a Konica Minolta CM-2300d spectrophotometer. The sections were dried before measurement.
The first table lists relevant detection data, and according to test characterization data, it can be seen that when the nano-supported titanium-based composite catalyst is used, the viscosity of the product is higher than that of the common titanium catalyst within the same reaction time, which indicates that the catalytic activity of the composite catalyst is higher, and meanwhile, the b value of the product is lower than that of the common titanium catalyst, and the hue is better. The viscosity of polyester produced by using the catalyst has small fluctuation, which shows that the molecular weight range of the product is stable.
TABLE-Properties of the PET products synthesized with different catalysts
Claims (10)
1. A preparation method of a nano-loaded titanium composite catalyst is characterized by comprising the following steps:
dissolving a titanium compound, tetraethoxysilane and a hydrolytic agent in absolute ethyl alcohol, and stirring and reacting for a certain time at room temperature to obtain a mixed solution;
adding metal salt into the mixed solution, continuously stirring, heating to volatilize the redundant solvent, and obtaining gel; the metal salt is one or more of chlorides, acetates or phosphates of Mg, Al, Mn, Co and Zn;
and thirdly, performing supercritical drying on the gel in the presence of a supercritical medium to obtain the final nano-loaded titanium composite catalyst.
2. The method for producing a nano-supported titanium-based composite catalyst according to claim 1,
in the first step, the reaction time is 1-4 h.
3. The method for producing a nano-supported titanium-based composite catalyst according to claim 1 or 2,
in the first step, the titanium compound is one or a mixture of more of n-butyl titanate, tetraethyl titanate, diisopropyl titanate, tetraisopropyl titanate, tetramethyl titanate and tetraoctyl titanate;
the hydrolytic agent is water, or the hydrolytic agent is water and one or more selected from acetic acid, lactic acid, hydrochloric acid, phosphoric acid, malic acid and citric acid.
4. The method for producing a nano-supported titanium-based composite catalyst according to any one of claims 1 to 3,
in the first step, the molar ratio of the titanium compound to the tetraethoxysilane is 1-30:1, preferably 5-20: 1;
the molar ratio of the titanium compound to the hydrolytic agent is 1:2-15, preferably 1: 5-10;
the molar ratio of the titanium compound to the absolute ethyl alcohol is 1:2-20, preferably 1: 5-10.
5. The method for producing a nano-supported titanium-based composite catalyst according to any one of claims 1 to 4,
and in the second step, after the metal salt is added, stirring for 1-2 hours at room temperature, then heating to 40-100 ℃, and performing ultrasonic dispersion until the gel is formed.
6. The method for producing a nano-supported titanium-based composite catalyst according to any one of claims 1 to 5,
in the second step, the molar ratio of the titanium compound to the metal cation of the compound metal salt is 20-1: 1; preferably 10-3: 1.
7. The method for producing a nano-supported titanium-based composite catalyst according to any one of claims 1 to 6,
in the third step, the supercritical medium is carbon dioxide, methanol or ethanol; more preferably ethanol; the supercritical drying time is 0.5-2 h.
8. A nano-supported titanium-based composite catalyst prepared by the method according to any one of claims 1 to 7.
9. The nano-supported titanium-based composite catalyst according to claim 8, wherein the main component is a nano-particle formed by supporting nano-titanium dioxide and a metal salt or a metal oxide on nano-silica; preferably, the particle size of the nanoparticles is 10 to 500nm, more preferably 20 to 200 nm.
10. The use of the nano-supported titanium-based composite catalyst according to claim 8 or 9 in polyester synthesis; preferably, the catalyst is used in an amount of 5 to 100ppm, more preferably 10 to 50ppm, calculated as the mass ratio of the titanium content in the catalyst to the finished polyester product.
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