CN116371467A - Preparation method and application of solid acid catalyst loaded with acidic ionic liquid - Google Patents

Abstract

The invention discloses a preparation method and an application thereof of a solid acid catalyst loaded with an acidic ionic liquid. It mixes sodium 4-hydroxybenzenesulfonate and formaldehyde, then adds the ionic liquid, and puts it in a flask with a reflux condenser under reflux conditions. The reaction is carried out, and after the reaction is completed, cooling is added, water is added, the precipitate is recovered, dried, ground and washed to obtain a solid acid catalyst loaded with ionic liquid. The stability and activity of the catalyst are improved, and it can be reused after simple filtration.

Description

Preparation method and application of a solid acid catalyst loaded with acidic ionic liquid

technical field

The invention belongs to the technical field of catalyst preparation, and in particular relates to a preparation method and application of a solid acid catalyst loaded with acidic ionic liquid.

Background technique

Esterification of acid alcohols strives to use the least amount of homogeneous acidic catalyst. The academic circles have achieved certain results in this aspect, but the esterification reaction still faces the challenge of using more efficient, simple and green catalysts.

In recent years, new green catalysts that have replaced traditional inorganic acids in esterification reactions have been developed and reported one after another. Among them, the application of acidic ionic liquids (IL) as catalysts in esterification reactions has attracted attention. As the reaction progresses, the ester products It can automatically stratify with the catalyst IL and promote the positive shift of the equilibrium. The acidic ionic liquid has achieved remarkable results in the catalytic esterification reaction, but the catalyst exists in the form of a liquid, which can only be recovered by complex vacuum distillation, and the reaction process requires The use of large amounts of expensive ionic liquids is not in line with optimal economic principles.

Contents of the invention

The purpose of this section is to outline some aspects of embodiments of the invention and briefly describe some preferred embodiments. Some simplifications or omissions may be made in this section, as well as in the abstract and titles of this application, to avoid obscuring the purpose of this section, abstract and titles, and such simplifications or omissions should not be used to limit the scope of the invention.

As one aspect of the present invention, the present invention provides a preparation method of a solid acid catalyst loaded with an acidic ionic liquid, which comprises: putting crosslinked polyvinylpyrrolidone powder into toluene, and adding 1,3 propane sultone. The mixture was stirred continuously under reflux at 80°C for 24 hours. The resulting solid zwitterions were recovered by filtration, washed with ethyl acetate, and then vacuum dried overnight to obtain the sample [PVPP-PS]. Grind and disperse the prepared [PVPP-PS] into ethyl acetate in a mortar, add sulfuric acid and stir for 24 hours, then filter and wash the mixture three times with ethanol, and dry in vacuum at 60°C to obtain the final product [PVPP-PS]HSO ₄ as a solid acid catalyst.

As the preparation method of the solid acid catalyst supporting acidic ionic liquid according to the present invention, it is characterized in that: the crosslinked polyvinylpyrrolidone and 1,3 propane sultone are mixed, wherein the crosslinked polyvinylpyrrolidone And the molar ratio of 1,3 propane sultone is 1:1.

As a preferred solution of the preparation method of the acidic ionic liquid-loaded solid acid catalyst of the present invention: adding sulfuric acid and stirring for 24 hours, wherein the mass ratio of sulfuric acid to the sample [PVPP-PS] is 18:1.

As a preferred solution of the preparation method of the acidic ionic liquid-loaded solid acid catalyst of the present invention: the reaction is carried out under reflux conditions, and the reaction time is 24 hours.

As a preferred solution of the preparation method of the acidic ionic liquid-loaded solid acid catalyst of the present invention: the washing is washing with ethyl acetate.

As a preferred version of the preparation method of the solid acid catalyst supporting acidic ionic liquid of the present invention: the solid acid, its preparation method is: under nitrogen atmosphere, put the cross-linked polyvinylpyrrolidone powder in toluene , After a while, add 1,3 propane sultone. The mixture was heated to 80 °C and stirred continuously for 24 hours in a 100 mL flask. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60° C. overnight to obtain a sample [PVPP-PS].

As a preferred solution of the preparation method of the acidic ionic liquid-loaded solid acid catalyst of the present invention: the solvent is ethyl acetate.

酸性离子液体H₂SO₄的固体酸催化剂及其制备方法。本发明制备的固体酸作为一种催化剂，可以催化乙酸和乙醇反应合成乙酸乙酯，具有较高的催化活性和稳定性。单独使用固体酸催化剂容易在反应中酸位点失活，从而造成反应活性下降，而负载/>

酸性离子液体的固体酸催化剂，固体酸包裹/>

酸性离子液体，使得催化剂稳定性和活性得到提升，负载/>

酸性离子液体后的催化剂催化性能比单纯的固体酸催化剂有着明显的提升，说明负载离子液体对提高催化性能有着促进作用。制备的催化剂其催化活性高，并且经过简单的过滤就可以重复利用。Beneficial effects of the present invention: the present invention provides a load

Solid acid catalyst of acidic ionic liquid _H2SO4 and preparation _method thereof. As a catalyst, the solid acid prepared by the invention can catalyze the reaction of acetic acid and ethanol to synthesize ethyl acetate, and has high catalytic activity and stability. Using a solid acid catalyst alone is easy to deactivate the acid site in the reaction, resulting in a decrease in reactivity, and the load/>

Solid acid catalyst of acidic ionic liquid, solid acid coating/>

Acidic ionic liquid, which improves the stability and activity of the catalyst, supports

The catalytic performance of the catalyst after the acidic ionic liquid is significantly improved compared with the pure solid acid catalyst, which shows that the supported ionic liquid can promote the improvement of the catalytic performance. The prepared catalyst has high catalytic activity and can be reused after simple filtration.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the drawings that need to be used in the description of the embodiments. in:

酸性离子液体固体酸催化剂的红外谱图。Fig. 1 is the load that embodiment 1 prepares

Infrared spectrum of acidic ionic liquid solid acid catalyst.

酸性离子液体催化合成乙酸乙酯的结果，横坐标为时间，纵坐标为乙酸乙酯收率。Fig. 2 is the load prepared by using each embodiment respectively

The result of the acidic ionic liquid catalyzed synthesis of ethyl acetate, the abscissa is time, and the ordinate is the yield of ethyl acetate.

酸性离子液体后的固体酸催化剂的催化稳定性对比图。Fig. 3 is the solid acid and load prepared by embodiment 3

Comparison of catalytic stability of solid acid catalysts after acidic ionic liquids.

Detailed ways

In order to make the above objects, features and advantages of the present invention more comprehensible, the specific implementation of the present invention will be described in detail below in conjunction with specific examples.

In the following description, a lot of specific details are set forth in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described here, and those skilled in the art can do it without departing from the meaning of the present invention. By analogy, the present invention is therefore not limited to the specific examples disclosed below.

Example 1:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。In a 100mL flask, under a nitrogen atmosphere, cross-linked polyvinylpyrrolidone powder (22.23g, the molar weight of the monomer is 0.2mol, purchased from Aladdin, product number P101410) was placed in toluene, and after a period of time, 1,3 propane was added sultone (6.8 g, 0.05 mol), and the mixture was heated to 80° C. and stirred continuously for 24 hours. The resulting solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain cross-linked polyvinylpyrrolidone: 1,3 propane sultone A solid acid [PVPP-PS] with a molar ratio of 1:0.25, 1 g of the obtained [PVPP-PS] was ground in a mortar, dispersed in ethyl acetate solution, and then sulfuric acid (5.0 g, 0.05 mol) was added to the solution and stirred for 24 h, upon completion, the mixture was filtered and washed three times with methanol, then the water and methanol were removed in vacuo at 60 °C to obtain the final product loaded

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

Esterification reaction (conducted in a reaction kettle): the reflux distillation method without water separation is adopted, the heating device is heated by a dimethyl silicone oil bath oil bath without an open flame and no contact with the heat source, the water at room temperature is condensed, and the magnetic stirrer is installed, connected First add acetic acid to the three-necked flask with the condenser tube and thermometer, and then raise the temperature to 80 degrees Celsius to add the catalyst. When the temperature reaches 80 degrees Celsius, add ethanol, turn on the magnetic stirrer, and start the reaction. The esterification reaction methods of Examples 1-5 and Comparative Examples 1-5 are the same as in this example. The experiment was repeated three times to obtain the average value.

Esterification product analysis: in the classic reaction of acetic acid and ethanol, the main products are ethyl acetate and water. Therefore, the experiment uses the reduction of the reactant acetic acid and the increase of ethyl acetate to characterize the progress of the experiment, and to provide a basis for the follow-up Calculations provide data support.

The gas chromatograph used in this experiment is GC-3420A produced by Beifen Rayleigh, the separation column used is a capillary column, the column parameters are 30m*0.32mm*0.50um, the detector is a hydrogen flame ionization detector, and the initial column temperature is 80 degrees Celsius , the temperature of the injector is 220 degrees Celsius, the temperature of the detector is 250 degrees Celsius, the temperature rise program is to keep at 80 degrees Celsius for 2 minutes, then rise to 200 degrees Celsius at a rate of 30 degrees Celsius per minute, and keep it for 5 minutes after rising to 200 degrees Celsius. During the preparation of the experiment, a mixed liquid of ethyl acetate, ethanol and acetic acid with a ratio of 15:3:1 was prepared, and the mixed liquid was taken and analyzed by gas chromatography, and the peak time of each component was calibrated. At the beginning of the reaction, use a pipette gun to adjust to 250 μL, quickly remove the sample, place the sample and quickly transfer it to the chromatographic chamber, and perform gas chromatographic analysis to test its content ratio. During the reaction process, a sample was taken every 20 minutes, and quickly transferred to the chromatographic chamber for gas chromatography analysis to test the content ratio of each component. During gas chromatographic analysis, rinse the needle tube more than 8 times repeatedly, and absorb 0.6 μL of the liquid to be tested when sampling. From the sampling of the three-necked flask to the chromatographic analysis and injection into the chromatograph, the total time should not exceed 1 minute to control the accuracy of the test. The esterification product analysis method and detection method of the following examples are all the same as the present example except for the description.

The yield of ethyl acetate in this embodiment is 64.2%±0.74%.

Example 2:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。In a 100mL flask, under a nitrogen atmosphere, cross-linked polyvinylpyrrolidone powder (11.11g, the molar weight of the monomer is 0.1mol) was put into toluene, and after a period of time, 1,3 propane sultone (6.8g, 0.05mol), the mixture was heated to 80°C and stirred continuously for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain a solid acid [PVPP-PS] with a molar ratio of 1:0.5. Take 1g of the prepared [PVPP-PS] and grind it evenly in a mortar, then disperse the sample into the ethyl acetate solution, then add sulfuric acid (5.0g, 0.05mol) into the solution, stir for 24h, after completion , the mixture was filtered and washed three times with methanol, then water and methanol were removed in vacuo at 60 °C to obtain the final product loading

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

The yield of ethyl acetate in this embodiment is 68.5%±1.3%.

Example 3:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。In a 100mL flask, under a nitrogen atmosphere, put cross-linked polyvinylpyrrolidone powder (5.55g, the molar weight of the monomer is 0.05mol, purchased from Aladdin, product number P101410) into toluene, after a period of time, add 1,3 Propane sultone (6.8 g, 0.05 mol), the mixture was heated to 80° C. and stirred continuously for 24 hours. The resulting solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain cross-linked polyvinylpyrrolidone: 1,3 propane sultone Solid acid [PVPP-PS] with a molar ratio of 1:1. Take 1g of the prepared [PVPP-PS] and grind it evenly in a mortar, then disperse the sample into the ethyl acetate solution, then add sulfuric acid (5.0g, 0.05mol) into the solution, stir for 24h, after completion , the mixture was filtered and washed three times with methanol, then water and methanol were removed in vacuo at 60 °C to obtain the final product loading

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

The yield of ethyl acetate in this embodiment is 82.3%±0.22%.

Esterification reaction (conducted in a reaction kettle): the reflux distillation method without water separation is adopted, the heating device is heated by a dimethyl silicone oil bath oil bath without an open flame and no contact with the heat source, the water at room temperature is condensed, and the magnetic stirrer is installed, connected First add acetic acid to the three-necked flask with the condenser tube and thermometer, and then raise the temperature to 80 degrees Celsius to add the catalyst. When the temperature reaches 80 degrees Celsius, add ethanol, turn on the magnetic stirrer, and start the reaction. The esterification reaction methods of Examples 1-5 and Comparative Examples 1-5 are the same as in this example. The experiment was repeated three times to obtain the average value.

Esterification product analysis: in the classic reaction of acetic acid and ethanol, the main products are ethyl acetate and water. Therefore, the experiment uses the reduction of the reactant acetic acid and the increase of ethyl acetate to characterize the progress of the experiment, and to provide a basis for the follow-up Calculations provide data support.

The gas chromatograph used in this experiment is GC-3420A produced by Beifen Rayleigh, the separation column used is a capillary column, the column parameters are 30m*0.32mm*0.50um, the detector is a hydrogen flame ionization detector, and the initial column temperature is 80 degrees Celsius , the temperature of the injector is 220 degrees Celsius, the temperature of the detector is 250 degrees Celsius, the temperature rise program is to keep at 80 degrees Celsius for 2 minutes, then rise to 200 degrees Celsius at a rate of 30 degrees Celsius per minute, and keep it for 5 minutes after rising to 200 degrees Celsius. During the preparation of the experiment, a mixed liquid of ethyl acetate, ethanol and acetic acid with a ratio of 15:3:1 was prepared, and the mixed liquid was taken and analyzed by gas chromatography, and the peak time of each component was calibrated. At the beginning of the reaction, use a pipette gun to adjust to 250 μL, quickly remove the sample, place the sample and quickly transfer it to the chromatographic chamber, and perform gas chromatographic analysis to test its content ratio. During the reaction process, a sample was taken every 20 minutes, and quickly transferred to the chromatographic chamber for gas chromatography analysis to test the content ratio of each component. During gas chromatographic analysis, rinse the needle tube more than 8 times repeatedly, and absorb 0.6 μL of the liquid to be tested when sampling. From the sampling of the three-necked flask to the chromatographic analysis and injection into the chromatograph, the total time should not exceed 1 minute to control the accuracy of the test.

Example 4:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。In a 100mL flask, under a nitrogen atmosphere, cross-linked polyvinylpyrrolidone powder (4.55g, the molar weight of the monomer is 0.041mol) was put into toluene, and after a period of time, 1,3 propane sultone (6.8g, 0.05mol), the mixture was heated to 80°C and stirred continuously for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain a solid acid [PVPP-PS] with a molar ratio of 1:1.2. Take 1g of the prepared [PVPP-PS] and grind it evenly in a mortar, then disperse the sample into the ethyl acetate solution, then add sulfuric acid (5.0g, 0.05mol) into the solution, stir for 24h, after completion , the mixture was filtered and washed three times with methanol, then water and methanol were removed in vacuo at 60 °C to obtain the final product loading

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

The yield of ethyl acetate in this embodiment is 80.5%±0.61%.

Example 5:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。In a 100mL flask, under a nitrogen atmosphere, cross-linked polyvinylpyrrolidone powder (3.7g, the molar weight of the monomer is 0.033mol) was put into toluene, and after a period of time, 1,3 propane sultone (6.8g, 0.05mol), the mixture was heated to 80°C and stirred continuously for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain a solid acid [PVPP-PS] with a molar ratio of 1:1.5. Take 1g of the prepared [PVPP-PS] and grind it evenly in a mortar, then disperse the sample into the ethyl acetate solution, then add sulfuric acid (5.0g, 0.05mol) into the solution, stir for 24h, after completion , the mixture was filtered and washed three times with methanol, then water and methanol were removed in vacuo at 60 °C to obtain the final product loading

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

The yield of ethyl acetate in this embodiment is 72.4%±1.02%.

Embodiment 6:

酸性离子液体的固体酸催化剂[PVPP-PS]HSO₄。Take 1g of [PVPP-PS] prepared in Example 3 with a molar ratio of 1,3 propane sultone: 1:1 [PVPP-PS], grind it evenly in a mortar, and disperse it into ethyl acetate solution , then sulfuric acid (5.0 g, 0.05 mol) was added to the solution and stirred for 24 h. After completion, the mixture was filtered and washed three times with methanol, and then water and methanol were removed in vacuum at 60° C. to obtain the final product supported

Solid acid catalyst of acidic ionic liquid [PVPP-PS]HSO ₄ .

Esterification reaction (rectification tower): The prepared solid acid catalyst loaded with ionic liquid is packed into the packed rectification tower, and the whole packed column is filled. The feed molar ratio of ethanol and acetic acid is Under the conditions of 1.2:1, the reaction temperature is 85 ℃, the reaction is carried out for 2 hours, and the catalytic effect of the solid acid catalyst is explored. The ethyl acetate yield was calculated according to the method of Example 1.

The yield of ethyl acetate in this embodiment is 95.6%±0.37%.

Embodiment 7:

In a 100mL flask, under a nitrogen atmosphere, put cross-linked polyvinylpyrrolidone powder (5.55g, the molar weight of the monomer is 0.05mol, purchased from Aladdin, product number P101410) into toluene, after a period of time, add 1,3 Propane sultone (6.8 g, 0.05 mol), the mixture was heated to 80° C. and stirred continuously for 24 hours. The resulting solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60°C overnight to obtain cross-linked polyvinylpyrrolidone: 1,3 propane sultone Solid acid [PVPP-PS] with a molar ratio of 1:1.

Ethyl acetate was prepared by the esterification reaction method of the method in Example 1, and the ethyl acetate yield was calculated.

The yield of ethyl acetate in this embodiment is 66.3%±0.91%.

Comparative example 1:

In a 100mL flask, 2-picoline (4.65g, monomer molar weight is 0.05mol) was put into toluene under nitrogen atmosphere, and after a period of time, 1,3 propane sultone (6.8g, 0.05mol ), the mixture was heated to 80°C and stirred continuously for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60° C. overnight to obtain a solid acid [CHNO-PS] catalyst.

Ethyl acetate was prepared by the esterification reaction method of the method in Example 1, and the ethyl acetate yield was calculated.

The yield of ethyl acetate in this embodiment is 55.1%±0.46%.

Comparative example 2:

In a 100mL flask, imidazole (3.4g, monomer molar weight: 0.05mol) was put into toluene under a nitrogen atmosphere, after a period of time, 1,3 propane sultone (6.8g, 0.05mol) was added, and the mixture Heating to 80°C continued stirring for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60° C. overnight to obtain a solid acid [Bmim-PS] catalyst.

Ethyl acetate was prepared by the esterification reaction method of the method in Example 1, and the ethyl acetate yield was calculated.

The yield of ethyl acetate in this embodiment is 60.2%±0.83%.

Comparative example 3:

In a 100mL flask, m-aminobenzenesulfonic acid (8.66g, monomer molar weight: 0.05mol) was put into toluene under a nitrogen atmosphere, and after a period of time, 1,3 propane sultone (6.8g, 0.05 mol), the mixture was heated to 80°C and stirred continuously for 24 hours. The obtained solid zwitterions were recovered by filtration, washed with ethyl acetate to completely remove unreacted reactants, and then dried under vacuum at 60° C. overnight to obtain a solid acid [3-AMSA-PS] catalyst.

Ethyl acetate was prepared by the esterification reaction method of the method in Example 1, and the ethyl acetate yield was calculated.

The yield of ethyl acetate in this embodiment is 50.5%±0.36%.

Comparative example 4:

酸性离子液体的固体酸催化剂[PVPP-PS]H₂PO₄。After the [PVPP-PS] prepared in a ratio of 1:1 obtained in Example 3 was uniformly ground in a mortar, 1 g was dispersed into an ethyl acetate solution, and then phosphoric acid (4.9 g, 0.05 mol) was added to the solution, Stirring for 24 h, upon completion, the mixture was filtered and washed three times with methanol, then the water and methanol were removed in vacuo at 60 °C to obtain the final product loading

Solid acid catalyst of acidic ionic liquid [PVPP-PS]H ₂ PO ₄ .

The ethyl acetate yield of this embodiment is 74.5% ± 0.51%.

Comparative example 5:

酸性离子液体的固体酸催化剂[PVPP-PS]BF₄。After grinding the [PVPP-PS] obtained in Example 3 at a ratio of 1:1 in a mortar, take 1 g and disperse it into the ethyl acetate solution, then add fluoroboric acid (4.39 g, 0.05 mol) into the solution , stirred for 24 h, upon completion, the mixture was filtered and washed three times with methanol, then water and methanol were removed in vacuo at 60 °C to obtain the final product loaded

Solid acid catalyst [PVPP-PS]BF ₄ of acidic ionic liquid.

Ethyl acetate was prepared by the esterification reaction method of the method in Example 1, and the ethyl acetate yield was calculated.

The yield of ethyl acetate in this embodiment is 65.4%±0.24%.

酸性离子液体的固体酸催化剂及其制备方法。本发明制备的负载/>

酸性离子液体的固体酸催化剂作为一种催化剂，可以催化乙酸和乙醇反应合成乙酸乙酯，具有较高的催化活性和稳定性。单独使用离子液体的液体催化剂容易在反应中分解，从而造成反应活性下降，而负载离子液体的固体酸催化剂，固体酸包裹离子液体，使得催化剂稳定性和活性得到提升，负载离子液体后的催化剂催化性能比单纯的固体酸催化剂有着显著的提升(实验结果具有统计学差异)。制备的固体酸其催化活性高，并且经过简单的过滤就可以重复利用。The present invention provides a load

Solid acid catalyst of acidic ionic liquid and preparation method thereof. The load prepared by the present invention/>

The solid acid catalyst of the acidic ionic liquid, as a catalyst, can catalyze the reaction of acetic acid and ethanol to synthesize ethyl acetate, and has high catalytic activity and stability. The liquid catalyst using ionic liquid alone is easy to decompose in the reaction, resulting in a decrease in reactivity, while the solid acid catalyst loaded with ionic liquid, the solid acid wraps the ionic liquid, which improves the stability and activity of the catalyst, and the catalyst after loading the ionic liquid catalyzes Compared with the pure solid acid catalyst, the performance is significantly improved (the experimental results have statistical differences). The prepared solid acid has high catalytic activity and can be reused after simple filtration.

It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention without limitation, although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be carried out Modifications or equivalent replacements without departing from the spirit and scope of the technical solution of the present invention shall be covered by the claims of the present invention.

Claims (9)

1. a kind of preparation method of the solid acid catalyst of load acidic ionic liquid, it is characterized in that: cross-linked polyvinylpyrrolidone powder is put into toluene, add 1,3 propane sultone obtains mixture, described mixture is in Stir the reaction under heating and reflux conditions, filter and recover the obtained amphoteric solid ions, wash, and vacuum dry overnight to obtain a solid [PVPP-PS] catalyst, and grind the solid [PVPP-PS] catalyst in a mortar and disperse it in the solvent, Add sulfuric acid and stir for 20-30 hours, filter, wash, and vacuum-dry to obtain [PVPP-PS]HSO ₄ solid acid catalyst. 2. The preparation method of the solid acid catalyst supporting acidic ionic liquid according to claim 1, characterized in that: the molar ratio of cross-linked polyvinylpyrrolidone to 1,3 propane sultone is 1:1. 3. the preparation method of the solid acid catalyst of supporting acidic ionic liquid according to claim 1 or 2, is characterized in that: described adding sulfuric acid, wherein, the mass ratio of sulfuric acid and solid [PVPP-PS] catalyst is 18:1 . 4. The preparation method of the acidic ionic liquid-loaded solid acid catalyst according to claim 1 or 2, characterized in that: the stirring reaction is carried out under heating and reflux conditions, the reaction temperature is 80° C., and the reaction time is 24 hours. 5. The preparation method of the solid acid catalyst loaded with acidic ionic liquid according to claim 1 or 2, characterized in that: the obtained amphoteric solid ions are recovered by filtration and washed by washing with ethyl acetate. 6 . The preparation method of the acidic ionic liquid-loaded solid acid catalyst according to claim 1 or 2, characterized in that: the vacuum drying overnight is vacuum drying at 60° C. overnight. 7. The preparation method of the solid acid catalyst supporting acidic ionic liquid according to claim 6, characterized in that: the solvent is ethyl acetate. 8. the application of the solid acid catalyst of the loaded acidic ionic liquid obtained by the preparation method of claim 1 as an esterification catalyst. 9. The application according to claim 8, characterized in that: in the esterification reaction, the reaction substrates are acetic acid and ethanol.

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