A method for preparing a supported esterification reaction catalyst and catalyst and application thereof

Abstract

The present invention relates to the technical field of catalyst preparation, and specifically to a method for preparing a supported esterification reaction catalyst, a catalyst, and an application thereof, comprising the following steps: S1. synthesizing magnesium aluminum spinel carrier particles; S2. preparing a catalyst precursor, adding a metal hydroxide solution to the magnesium aluminum spinel carrier particles, then adding a cationic active agent, washing, filtering, and drying to obtain a cation-modified catalyst precursor; S3. preparing a catalyst, adding an active agent and an HCl solution to the cation-modified catalyst precursor, stirring, washing, filtering, and drying to obtain the desired esterification reaction catalyst. The magnesium aluminum spinel structure of the catalyst provides the catalyst with better chemical stability and thermodynamic stability, and also has a greater impact on the catalyst strength and service life. Ultimately, a high yield of cyclic carbonate can be obtained under mild reaction conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst preparation, and in particular to a method for preparing a supported esterification reaction catalyst, the catalyst and application thereof. Background Art

[0002] Cyclic carbonates are important green chemical raw materials with a wide range of uses. They can be used as solvents, gasoline additives, etc. They are also important raw materials for the synthesis of dibasic carbonates. Currently, many researchers at home and abroad are actively studying and promoting new methods for the synthesis of cyclic carbonates. Among them, the most widely used method is to use carbon dioxide, which is widely available and inexpensive, as a raw material and synthesize cyclic carbonates through esterification with cycloalkanes.

[0003] A key factor influencing the development of technologies for synthesizing cyclic carbonates through esterification of cycloalkanes is the development of efficient catalysts. Homogeneous catalysts, typically quaternary ammonium salts, have attracted considerable attention due to their rapid reaction rates and high product yields. However, homogeneous catalysts are difficult to separate from the product, resulting in high operating costs and poor stability, making their widespread adoption difficult. Currently, heterogeneous catalysts, developed to address the difficulties encountered by homogeneous catalysts, can effectively address the challenges of catalyst separation and recovery. However, these catalysts exhibit low selectivity and yield for the target product.

[0004] For example, invention patent CN201910976767.0 conducts an esterification reaction between ethylene oxide and carbon dioxide in a single-stage or multi-stage bubbling tower, and obtains 99.9w% ethylene carbonate through stripping and refining units. However, because this invention patent uses a homogeneous catalyst, a more complex catalyst recovery device must be added. Therefore, the investment cost and operating cost of this invention are high, and the separation effect of the homogeneous catalyst is poor, making it difficult to achieve 100% recovery. At the same time, a very small amount of residue in the product ethylene carbonate will also affect the purity and quality of the product. Invention patent CN202110294426.2 invents a device and method for producing an electronic-grade ethylene carbonate product with a purity of 99.99%. This invention patent also uses an ionic liquid homogeneous catalyst and also requires a catalyst recovery device. Due to the poor stability of the homogeneous catalyst, a portion of the deactivated catalyst must be continuously discharged; and the homogeneous catalyst is difficult to separate, resulting in unnecessary loss, so new homogeneous catalyst needs to be continuously added. In summary, there is an urgent need to develop highly active and stable heterogeneous (i.e., supported) esterification catalysts.

[0005] For example, the invention patent (CN200910114260.0) successfully developed active components, chloride and iodine salt, which were filtered through deionized water multiple times, dissolved and dried, and then loaded onto SiO2 or activated carbon carriers. After tableting and screening, a supported bimetallic complex was obtained as an esterification catalyst. However, the ethylene oxide conversion rate and ethylene carbonate selectivity in the low-temperature reaction zone (120°C) and low-pressure zone (2Mpa) were both low. Therefore, there are still technical bottlenecks in the development of heterogeneous catalyst technology, which require key breakthroughs. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a supported esterification reaction catalyst, a catalyst and an application thereof, so as to solve the technical problems in the prior art of low heat exchange efficiency of the liquid in the reactor, uneven heat distribution, slow temperature adjustment and control, low product yield and difficulty in achieving automation.

[0007] The present invention discloses a method for preparing a supported esterification reaction catalyst, comprising the following steps:

[0008] S1. Synthetic magnesium aluminum spinel support particles;

[0009] S2. Preparation of catalyst precursor

[0010] Adding a metal hydroxide solution and a cationic active agent to the magnesium aluminum spinel support particles, followed by washing, filtering and drying to obtain a cation-modified catalyst precursor;

[0011] S3. Preparation of Catalyst

[0012] The cation-modified catalyst precursor is added to an active agent and an HCl solution, stirred, washed, filtered and dried to obtain the desired esterification reaction catalyst.

[0013] Furthermore, the synthesis method of the magnesium-aluminum spinel carrier particles is:

[0014] adding an acidic modifier to the base solution under stirring, controlling the pH value of the sol to be 6-9, and obtaining a mixed slurry;

[0015] The mixed slurry is used to wash the filter cake, and the obtained filter cake is dried to obtain a magnesia-alumina spinel precursor, which is then roasted, ground, pulverized, and sieved to obtain the desired magnesia-alumina spinel carrier particles.

[0016] Furthermore, after adding the acidic modifier, stirring is carried out at 15-40° C. for 0.1-4 h.

[0017] Furthermore, the filter cake is washed with deionized water at 40-99°C.

[0018] Furthermore, the calcination temperature is 450-700° C., and the calcination time is 1-8 hours.

[0019] Furthermore, the magnesium-aluminum spinel carrier particles are 40-120 μm particles.

[0020] Furthermore, the cationic active agent is octadecyltrimethylammonium bromide, 3-chloro-2-hydroxypropyltrimethylammonium chloride or dodecylbenzyltrimethylammonium chloride.

[0021] Furthermore, the washing, filtering and drying steps in step S2 are repeated 2-4 times.

[0022] Furthermore, after adding the cationic active agent, stirring is carried out at 25-60° C. for 0.1-4 hours.

[0023] Furthermore, the active auxiliary agent is a Zn salt solution or a metal oxide.

[0024] Furthermore, the molar concentration of the HCl solution is 0.1 mol / L.

[0025] A supported esterification reaction catalyst is prepared by the above method.

[0026] Furthermore, it includes magnesium aluminum spinel support, a cationic active agent and a metal oxide or a metal salt.

[0027] The invention discloses an application of a method for preparing a supported esterification reaction catalyst, which is used to prepare a catalyst for synthesizing cyclic carbonates by esterification of cycloalkanes.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The composition of the catalyst has a great influence on its catalytic performance and reaction mechanism. The stable state combination of the catalyst components can greatly improve and enhance the catalytic performance of the catalyst. In the present invention, a magnesium aluminum spinel support is modified and activated with a cationic active agent such as octadecyltrimethylammonium bromide, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and dodecylbenzyltrimethylammonium chloride, and then a metal salt or metal oxide is loaded on its surface. The resulting supported esterification reaction catalyst has a distinct stable state structure. This combination has excellent adsorption / desorption performance for the separation and purification of the reaction products.

[0030] 2. The specific surface area and pore volume of the catalyst are also important factors affecting its catalytic performance. At the same time, the stable structure can increase the specific surface area of ​​the catalyst and effectively improve the catalytic reaction activity of the active components of the catalyst - cationic activator and metal oxide / metal salt.

[0031] 3. The magnesium-aluminum spinel structure of the catalyst provides the catalyst with better chemical stability and thermodynamic stability, and also has a great influence on the strength and service life of the catalyst. Ultimately, a high yield of cyclic carbonate can be obtained under mild reaction conditions. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0033] In order to investigate the relevant performance of the catalyst of the present invention, the inventors pressed the prepared esterification reaction catalyst and sieved it to 20-40 mesh, and conducted relevant catalytic activity evaluation on the catalysts of each embodiment and comparative example. The evaluation method was as follows: using a kettle reactor, the molar ratio of ethylene oxide to carbon dioxide was 1:1.5, the reaction conditions were: ethylene oxide to catalyst mass ratio of 10:1, 2.5 MPa, and bed temperature controlled at 80-120°C.

[0034] Comparative Example 1

[0035] The preparation method of the catalyst of this comparative example is as follows:

[0036] Step A:

[0037] Weigh 100g Al2O3;

[0038] Step B:

[0039] The Al2O3 prepared in step A was mixed with 25 g of 1 mol / L sodium hydroxide solution and stirred evenly. 25 g of octadecyltrimethylammonium bromide solution as a cationic active agent was then added and stirred at 30°C for 2 h. The mixture was further washed, filtered and dried, and the above steps were repeated twice to obtain a cation-modified catalyst precursor.

[0040] Step C:

[0041] To the cation-modified catalyst precursor obtained in step B, 10 g of ZnCl2 solution or metal oxide and 2 g of 0.01 mol / L HCl solution were added, calculated as ZnO, and stirred at 30°C for 2 h. The mixture was further washed, filtered and dried to obtain the desired esterification reaction catalyst of Comparative Example 1.

[0042] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification activity evaluation. After 1 hour of reaction, the catalytic performance of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0043] Comparative Example 2

[0044] The preparation method of the catalyst of this comparative example is as follows:

[0045] Step A:

[0046] 100 g of pseudo-boehmite (calculated as Al2O3), 5 g of magnesium chloride (calculated as MgO), and 30 g of ammonia solution (calculated as Na2O) were weighed separately and stirred at 25°C for 0.5 h. Then, nitric acid solution was added dropwise under continuous stirring to control the pH value of the sol to be around 7. Stirring was continued for 2 h to obtain a mixed slurry.

[0047] Step B:

[0048] The mixed slurry obtained in step A is washed with deionized water at 60°C, and the obtained filter cake is dried at 100°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 500°C for 2 hours. Finally, it is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0049] Step C:

[0050] 30 g of octadecyltrimethylammonium bromide was added to the magnesium aluminum spinel carrier particles obtained in step B, and the mixture was stirred at 30° C. for 2 h, and then further washed, filtered and dried to obtain the desired catalyst for the esterification reaction in comparative example 2.

[0051] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0052] Example 1

[0053] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as follows:

[0054] Step A:

[0055] Weigh 100 g of sodium aluminate solution (calculated as Al2O3), 2 g of magnesium nitrate (calculated as MgO), and 30 g of sodium hydroxide solution (calculated as Na2O) respectively, stir at 30°C for 0.5 h, then add nitric acid solution dropwise under continuous stirring to control the pH value of the sol to be around 7, and continue stirring for 4 h to obtain a mixed slurry;

[0056] Step B:

[0057] The mixed slurry obtained in step A is washed with deionized water at 60°C, and the obtained filter cake is dried at 100°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 550°C for 2.5 hours. Finally, the precursor is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0058] Step C:

[0059] The magnesium aluminum spinel support particles obtained in step B were added to 20 g of sodium hydroxide solution calculated as Na2O, and then 80 g of octadecyltrimethylammonium bromide was added, and stirred at 40°C for 2 h, and further washed, filtered and dried, and the above steps were repeated 4 times to obtain a cation-modified catalyst precursor;

[0060] In this step, the hydroxide solution, the cationic active agent and the magnesium aluminum spinel support particles are dispersed under ultrasonic conditions;

[0061] Step D:

[0062] The cation-modified catalyst precursor obtained in step C was added with 10 g of ZnBr2 and stirred evenly. Then, a 0.01 mol / L HCl solution was added dropwise until the pH value of the solution was about 7. The mixture was then stirred at 30°C for 2.5 h, washed, filtered, and dried to obtain the desired catalyst for the esterification reaction in Example 1.

[0063] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0064] Example 2

[0065] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as follows:

[0066] Step A:

[0067] 100 g of pseudo-boehmite (calculated as Al2O3), 2 g of magnesium chloride (calculated as MgO), and 50 g of ammonia solution (calculated as Na2O) were weighed separately and stirred at 40°C for 4 h. Then, hydrochloric acid solution was added dropwise under continuous stirring to control the pH value of the sol to be around 9. Stirring was continued for 4 h to obtain a mixed slurry.

[0068] Step B:

[0069] The mixed slurry obtained in step A is washed with 40°C deionized water, and the obtained filter cake is dried at 120°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 450°C for 8 hours. Finally, it is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0070] Step C:

[0071] The magnesium aluminum spinel support particles obtained in step B were added to 20 g of potassium hydroxide solution calculated as Na2O, and 10 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added, and stirred at 60°C for 0.1 h, and further washed, filtered and dried. The above steps were repeated 4 times to obtain a cation-modified catalyst precursor;

[0072] In this step, the hydroxide solution, the cationic active agent and the magnesium aluminum spinel support particles are dispersed under ultrasonic conditions;

[0073] Step D:

[0074] 0.05 g of ZnCl2 was added to the cation-modified catalyst precursor obtained in step C, and after stirring evenly, a 0.01 mol / L HCl solution was continued to be added dropwise until the solution pH value was about 7. Then, the mixture was stirred at 60°C for 0.1 h, further washed, filtered and dried to obtain the desired esterification reaction catalyst of Example 2.

[0075] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0076] Example 3

[0077] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as follows:

[0078] Step A:

[0079] Weigh 90 g of aluminum chloride solution (based on Al2O3), 10 g of aluminum hydroxide solution (based on Al2O3), 0.5 g of magnesium hydroxide (based on MgO), 3 g of potassium hydroxide solution (based on Na2O), and 1 g of ammonia solution (based on Na2O) respectively, stir at 15°C for 0.1 h, then introduce carbon dioxide gas while stirring to control the pH of the sol to be around 6, and continue stirring for 0.5 h to obtain a mixed slurry;

[0080] Step B:

[0081] The mixed slurry obtained in step A is washed with 99°C deionized water, and the obtained filter cake is dried at 80°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 700°C for 1 hour. Finally, it is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0082] Step C:

[0083] The magnesium aluminum spinel support particles obtained in step B were added to 50 g of an ammonia solution calculated as Na2O, and then 5 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride and 5 g of dodecylbenzyltrimethylammonium chloride were added. The mixture was stirred at 25°C for 4 h, and then further washed, filtered and dried. The above steps were repeated twice to obtain a cation-modified catalyst precursor.

[0084] In this step, the hydroxide solution, the cationic active agent and the magnesium aluminum spinel support particles are dispersed under ultrasonic conditions;

[0085] Step D:

[0086] The cation-modified catalyst precursor obtained in step C was added with 20 g of ZnO and stirred evenly. 0.01 mol / L HCl solution was then added dropwise until the pH of the solution was about 7. The mixture was then stirred at 25° C. for 4 h, washed, filtered, and dried to obtain the catalyst of Example 3 for the esterification reaction.

[0087] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0088] Example 4

[0089] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as follows:

[0090] Step A:

[0091] Weigh 100 g of aluminum nitrate solution (calculated as Al2O3), 15 g of magnesium nitrate (calculated as MgO), and 30 g of sodium hydroxide solution (calculated as Na2O) respectively, stir at 30°C for 3 h, then introduce carbon dioxide gas while stirring continuously to control the pH value of the sol to be around 7, and continue stirring for 3 h to obtain a mixed slurry;

[0092] Step B:

[0093] The mixed slurry obtained in step A is washed with 99°C deionized water, and the obtained filter cake is dried at 110°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 600°C for 1.5 hours. Finally, it is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0094] Step C:

[0095] The magnesium aluminum spinel support particles obtained in step B were added to a potassium hydroxide solution with a mass of 10 g as Na2O, and then 80 g of octadecyltrimethylammonium bromide was added, and stirred at 50°C for 1 hour, and further washed, filtered and dried, and the above steps were repeated 3 times to obtain a cation-modified catalyst precursor;

[0096] In this step, the hydroxide solution, the cationic active agent and the magnesium aluminum spinel support particles are dispersed under ultrasonic conditions;

[0097] Step D:

[0098] The cation-modified catalyst precursor obtained in step C was added with 20 g ZnBr2 and 2 g ZnCl2, and after stirring evenly, a 0.01 mol / L HCl solution was continued to be added dropwise until the solution pH value was about 7, and then stirred at 50°C for 1 hour. The mixture was further washed, filtered and dried to obtain the desired esterification reaction catalyst of Example 4.

[0099] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0100] Example 5

[0101] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as follows:

[0102] Step A:

[0103] Weigh 100 g of aluminum nitrate solution (calculated as Al2O3), 1 g of magnesium nitrate (calculated as MgO), and 25 g of sodium hydroxide solution (calculated as Na2O) respectively, stir at 35°C for 3 h, then add nitric acid solution dropwise while stirring continuously, control the pH value of the sol to be around 7, and continue stirring for 2 h to obtain a mixed slurry;

[0104] Step B:

[0105] The mixed slurry obtained in step A is washed with deionized water at 60°C, and the obtained filter cake is dried at 105°C to obtain a magnesia-alumina spinel precursor, which is then placed in a muffle furnace and calcined at 520°C for 2.5 hours. Finally, it is ground and sieved to obtain 40-120 μm particles, which are the desired magnesia-alumina spinel carrier particles;

[0106] Step C:

[0107] The magnesium aluminum spinel support particles obtained in step B were added to a sodium hydroxide solution with a mass of 10 g as Na2O, and 50 g of octadecyltrimethylammonium bromide was added, and stirred at 40°C for 2 h, and further washed, filtered and dried, and the above steps were repeated 4 times to obtain a cation-modified catalyst precursor;

[0108] In this step, the hydroxide solution, the cationic active agent and the magnesium aluminum spinel support particles are dispersed under ultrasonic conditions;

[0109] Step D:

[0110] The cation-modified catalyst precursor obtained in step C was added with 20 g of ZnBr2 and stirred evenly. A 0.01 mol / L HCl solution was then added dropwise until the pH value of the solution was about 7. The mixture was then stirred at 40°C for 2 h, washed, filtered, and dried to obtain the catalyst of Example 5 for the desired esterification reaction.

[0111] The catalyst powder was pelletized and sieved, and particles with a mesh size of 20-40 were selected for esterification reaction activity evaluation. After 1 hour of reaction, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0112] Example 6

[0113] The preparation method of the magnesium aluminum spinel-supported cationic active agent and metal oxide / metal salt catalyst in this embodiment is as shown in Example 5:

[0114] After the catalyst was recycled for 5 times, it was loaded into the reaction activity evaluation device. After the reaction for 1 hour, the catalytic effect of the catalyst was analyzed by chromatography. The specific catalytic performance is shown in Table 1.

[0115] Table 1 Comparison of catalytic activity of catalysts

[0116]

[0117]

[0118] As can be seen from the table above, Comparative Example 1 does not use magnesium aluminum spinel support particles, and Comparative Example 2 does not use an activating agent, resulting in relatively poor catalytic effects. However, the examples show that the supported esterification catalyst prepared by the present invention can achieve high cycloalkane conversion and high thermodynamic stability. In Example 5, the ethylene oxide conversion reached 98%, and the ethylene carbonate yield reached 97%. In Example 6, the catalyst still exhibited excellent catalytic effects after being recycled five times.

[0119] The above are the implementation methods listed in this embodiment, but this embodiment is not limited to the above optional implementation methods. Those skilled in the art can arbitrarily combine the above methods to obtain other various implementation methods. Anyone can derive other various forms of implementation methods based on the inspiration of this embodiment. The above specific implementation methods should not be understood as limiting the scope of protection of this embodiment. The scope of protection of this embodiment shall be based on the definition in the claims, and the description can be used to interpret the claims.

Claims

1. A method for preparing a supported esterification catalyst, characterized in that: The following steps are involved: S1. Synthetic magnesium aluminate spinel support particles; S2. Preparation of catalyst precursor Adding a metal hydroxide solution and a cationic active agent to the magnesium aluminum spinel support particles, followed by washing, filtering and drying to obtain a cation-modified catalyst precursor; S3. Preparation of Catalyst Adding the cation-modified catalyst precursor to an active agent and an HCl solution, stirring, washing, filtering and drying to obtain the desired esterification reaction catalyst; The metal hydroxide is sodium hydroxide or potassium hydroxide; The cationic active agent is octadecyltrimethylammonium bromide, 3-chloro-2-hydroxypropyltrimethylammonium chloride or dodecylbenzyltrimethylammonium chloride; The active auxiliary agent is a Zn salt solution or a metal oxide.

2. The method for preparing a supported esterification catalyst according to claim 1, wherein: The synthesis method of the magnesium aluminum spinel carrier particles is: adding an acidic modifier to the base solution under stirring, controlling the pH value of the sol to be 6-9, and obtaining a mixed slurry; The mixed slurry is filtered, and the filter cake is washed. The obtained filter cake is dried to obtain a magnesia-alumina spinel precursor, which is then roasted, ground, pulverized, and sieved to obtain the desired magnesia-alumina spinel carrier particles.

3. The method for preparing a supported esterification catalyst according to claim 2, wherein: After adding the acidic modifier, stir at 15-40°C for 0.1-4h.

4. The method for preparing a supported esterification catalyst according to claim 2, wherein: The filter cake was washed with deionized water at 40-99°C.

5. The method for preparing a supported esterification catalyst according to claim 2, wherein: The calcination temperature is 450-700° C., and the calcination time is 1-8 hours.

6. The method for preparing a supported esterification catalyst according to claim 1, wherein: The magnesium aluminum spinel carrier particles are 40-120 μm particles.

7. A supported esterification catalyst, characterized in that: The method for preparing a supported esterification reaction catalyst according to any one of claims 1 to 6 is used.

8. Use of the catalyst prepared by the method for preparing a supported esterification catalyst according to any one of claims 1 to 6, characterized in that: Catalyst for the preparation of cycloalkanes for the esterification of cyclic carbonates.

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