Solid acid catalyst and preparation and application thereof

Abstract

The present application relates to the technical field of fine chemicals synthesis, in particular to a solid acid catalyst and its preparation and application. The present application firstly mixes tetrabutyl titanate solution and tetraethyl orthosilicate solution uniformly, then reacts after dropping ammonia water, ages and carries out post-treatment after the reaction is finished, and obtains a composite carrier TiO2-SiO2; the composite carrier TiO2-SiO2 is impregnated with a metal salt solution, and is subjected to steam drying, drying and calcination in sequence to obtain a solid acid catalyst; the solid acid catalyst prepared by the present application has the advantages of good specific selectivity, high catalytic activity, easy reuse, high stability and the like, and has the advantages of simple operation, fast reaction speed, high yield and the like when applied to succinic acid monomenthyl ester synthesis process.

Description

Technical Field

[0001] This invention relates to the field of fine chemical synthesis technology, and in particular to a solid acid catalyst and its preparation and application. Background Technology

[0002] Menthyl succinate is almost odorless, with only a cool, refreshing scent. It has a long-lasting cooling sensation in the mouth and a pleasant taste. Its applications are very broad, serving as a cooling agent in pharmaceuticals, tobacco, beverages, and daily chemical products.

[0003] There are two main routes for the synthesis of menthyl succinate: direct esterification and acylation. Direct esterification uses L-menthol and succinic acid as raw materials, and the reaction proceeds under the action of an acidic catalyst. The drawback of this method is its relatively low conversion rate and the generation of waste acid during the reaction. Acylation uses L-menthol and succinic anhydride, and the reaction proceeds under the action of a catalyst. This method yields a high product yield and produces fewer byproducts.

[0004] CN101823961A uses menthol and succinic anhydride to react at a certain temperature. After the reaction is complete, water is added and refluxed. Then, the mixture is extracted with ethyl acetate, the ethyl acetate is recovered, and the product, menthol monosuccinate, is obtained by recrystallization with petroleum ether.

[0005] CN105294436A uses DMAP as a catalyst and chloroform as a solvent to react menthol with succinic anhydride at a certain temperature. After the reaction is complete, the mixture is diluted with ethyl acetate, washed with 10% sodium carbonate, the aqueous layer is acidified with dilute hydrochloric acid, and then extracted with ethyl acetate to recover the solvent, thus obtaining the product menthol monosuccinate.

[0006] CN10738931B uses p-toluenesulfonic acid as a catalyst to react menthol with succinic anhydride at a certain temperature to obtain crude succinic anhydride monomenthyl ester, which is then separated by silica gel column chromatography to obtain the product succinic anhydride monomenthyl ester.

[0007] US7247743B1 uses an alkaline catalyst (sodium carbonate or sodium acetate) or no catalyst to react menthol with succinic anhydride at a certain temperature to obtain a mixture containing 88.6% monoester and 4.16% diester, or a mixture containing 84.6% monoester and 7.19% diester.

[0008] Based on currently available information, the synthesis of menthol monosuccinate employs an acylation method, using acidic catalysts such as p-toluenesulfonic acid, and basic catalysts such as sodium carbonate, sodium acetate, or DMAP. These are homogeneous catalysts, which present problems such as the inability to recycle them and the generation of wastewater during post-processing. Furthermore, DMAP is difficult to separate from the reaction solution (poorly soluble in water, readily soluble in organic solvents) and is toxic and has an ammonia-like odor; its presence in the product can cause quality issues. However, not using a catalyst leads to longer reaction times and higher diester content. Summary of the Invention

[0009] To address the issues of catalysts and post-processing in the existing synthesis process of menthyl succinate, the present invention aims to provide a solid acid catalyst and its preparation and application. The solid acid catalyst prepared by this invention exhibits advantages such as good selectivity, high catalytic activity, ease of reuse, and high stability. Its application in the synthesis process of menthyl succinate offers advantages such as simple operation, fast reaction rate, and high yield.

[0010] The objective of this invention can be achieved through the following technical solutions:

[0011] The first objective of this invention is to provide a method for preparing a solid acid catalyst, comprising the following steps:

[0012] (S1) Tetrabutyl titanate solution and tetraethyl orthosilicate solution are mixed, and then ammonia water is added dropwise to react. After the reaction is completed, the mixture is aged and post-treated to obtain composite support TiO2-SiO2.

[0013] (S2) The composite support TiO2-SiO2 prepared by the metal salt solution impregnation step (S1) is subjected to evaporation, drying and calcination treatment to obtain a solid acid catalyst;

[0014] The metal salt solution is selected from one of zirconium salt, cerium salt, tin salt, or zinc salt.

[0015] In one embodiment of the present invention, in step (S1), the amount of tetrabutyl titanate and tetraethyl orthosilicate added ensures that the molar ratio of titanium to silicon is 1:1 (the composite carrier TiO2-SiO2 has the largest surface area and pore volume, which can provide more active centers).

[0016] Ammonia solution was added dropwise until the pH of the solution reached 9–10.

[0017] During the reaction, the temperature is 25–30℃ and the time is 2–3 hours.

[0018] During the aging process, the temperature is -5 to -10℃ and the time is 5 to 10 hours.

[0019] In one embodiment of the present invention, the tetrabutyl titanate solution is an ethanol solution of tetrabutyl titanate, and the tetraethyl orthosilicate solution is an ethanol solution of tetraethyl orthosilicate.

[0020] The mass concentration of the ammonia water is 20-25%.

[0021] In one embodiment of the present invention, in step (S1), the post-processing is as follows: after aging, the precipitated solid is sequentially filtered, washed, dried, roasted, ground, and sieved.

[0022] In one embodiment of the present invention, the temperature during the drying process is 110–120°C;

[0023] During the roasting process, the temperature is 450-550℃ (preferably 500℃) and the time is 4-5 hours.

[0024] During the sieving process, the mesh size of the sieve is 20 to 40.

[0025] In one embodiment of the present invention, in step (S2), the zirconium salt is selected from zirconium nitrate dihydrate or zirconium dichloride octahydrate;

[0026] The cerium salt is selected from cerium nitrate;

[0027] The tin salt is selected from tin tetrachloride;

[0028] The zinc salt is selected from either zinc sulfate or zinc chloride.

[0029] In one embodiment of the present invention, in step (S2), when the metal salt is a zirconium salt, the zirconium loading is 12-18 wt%.

[0030] When the metal salt is a cerium salt, the cerium loading is 12–18 wt%.

[0031] When the metal salt is a tin salt, the tin loading is 14.5–20.5 wt%.

[0032] When the metal salt is a zinc salt, the zinc loading is 8.5–14.5 wt%.

[0033] In one embodiment of the present invention, when the metal salt is a zirconium salt, the zirconium loading is 16 wt%.

[0034] When the metal salt is a cerium salt, the cerium loading is 16 wt%.

[0035] When the metal salt is a tin salt, the tin loading is 18.5 wt%.

[0036] When the metal salt is a zinc salt, the zinc loading is 12.5 wt%.

[0037] In one embodiment of the present invention, in step (S2), the immersion time is 10 to 15 hours during the immersion process;

[0038] The temperature during the drying process is 110℃;

[0039] During the roasting process, the temperature is 700-800℃ (preferably 750℃) and the time is 4-5 hours.

[0040] The second objective of this invention is to provide a solid acid catalyst, characterized in that the solid acid catalyst is prepared by the above method, using TiO2-SiO2 as a composite support, and the active component is zirconium, cerium, tin or zinc.

[0041] A third objective of this invention is to provide the application of a solid acid catalyst in the preparation of menthyl succinate, wherein the solid acid catalyst is a solid acid catalyst.

[0042] The fourth object of the present invention is to provide a method for preparing menthyl succinate, comprising the following steps:

[0043] (A1) Succinic anhydride and solid acid catalyst were heated and melted, then mixed with menthol and reacted to obtain an intermediate product;

[0044]

[0045] (A2) After dissolving the intermediate product of step (A1), filter to recover the solid acid catalyst, heat the reaction solution and add water to continue the reaction, and then perform post-treatment to obtain menthol monosuccinate.

[0046] In one embodiment of the present invention, in step (A1), the molar ratio of succinic anhydride to menthol is 1 to 1.6:1; the mass ratio of solid acid catalyst to menthol is 1 to 4:100 (preferably, the mass ratio of solid acid catalyst to menthol is 1:50); during the reaction, the temperature is 110 to 140°C and the time is 2 to 5 hours.

[0047] In one embodiment of the present invention, in step (A1), the reaction is continuously stirred at a speed of 400-600 rpm, preferably 500 rpm.

[0048] The menthol is selected from D-menthol, L-menthol or D,L-menthol, preferably L-menthol.

[0049] In step (A2), the reaction is carried out at a temperature of 55–60°C for 2.5–3 hours.

[0050] In one embodiment of the present invention, in step (A2), the intermediate product is dissolved in a solvent selected from cyclohexane, toluene, or heptane;

[0051] The solid acid catalyst can be recycled and reused. If its activity decreases, it can be restored by calcination (at a temperature of 750°C for 4-5 hours).

[0052] In one embodiment of the present invention, the post-processing in step (A2) is specifically as follows:

[0053] After the reaction was completed, the aqueous layer was separated, the water was evaporated, and succinic acid was recovered; the solvent in the organic layer was recovered, and menthol succinic acid monomentyl ester was obtained by high-vacuum distillation.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] (1) The solid acid catalyst prepared by the present invention has the advantages of good product selectivity, high raw material conversion rate and easy reusability.

[0056] (2) In the acylation reaction of this invention, a solid acid catalyst is used, and the dispersion of TiO2 on the SiO2 surface can enhance MO. x The interaction between (metal oxide) and the composite support enhances MO x The dispersion threshold on the surface of the composite carrier improves MO. x The dispersed state of the solid acid catalyst increases the number of acid centers on its surface, enhances its acidity, and further improves its reaction activity. In addition, high-temperature calcination makes the acid centers mainly L-acids, which are beneficial to the synthesis of L-menthyl succinate because L-menthyl alcohol is a secondary alcohol and is not easily dehydrated in an L-acid environment. Due to the high catalytic activity and good thermal stability of the solid acid catalyst, it is superior to catalysts such as p-toluenesulfonic acid, sodium carbonate, sodium acetate, or DMAP in the synthesis of L-menthyl succinate.

[0057] (3) In the post-treatment of the acylation reaction, the present invention can convert all the excess succinic anhydride into succinic acid by adding water and hydrolyzing at a certain temperature, so that the raw materials are recovered and the product is purified.

[0058] (4) The preparation of mono-charged succinic acid esters using solid acid catalysts in this invention is simple to operate, has a simple process route, and is green and environmentally friendly. Attached Figure Description

[0059] Figure 1 The image shows the EDS diagram of the solid acid catalyst (16% Zr / TS-1) prepared in Example 1. Detailed Implementation

[0060] The present invention will now be described in detail with reference to specific embodiments.

[0061] In the following embodiments, the gas chromatography column used was KB-50 30m*0.32mm*1.00μm, and the integration method used was the area normalization method. Unless otherwise specified, all reagents used were commercially available, and all detection methods and techniques used were conventional detection methods and techniques in the field.

[0062] Example 1

[0063] This embodiment provides a method for preparing the composite support TiO2-SiO2, specifically including the following steps:

[0064] (1) Dissolve 34.0g of tetrabutyl titanate in 310g of ethanol to obtain a tetrabutyl titanate ethanol solution;

[0065] 15.0 g of ethyl silicate (containing 40% SiO2) was dissolved in 10 g of ethanol to obtain an ethyl silicate ethanol solution.

[0066] (2) Under stirring, the tetrabutyl titanate ethanol solution and the ethyl silicate ethanol solution prepared in step (1) are mixed evenly, and then 25wt% ammonia water is added dropwise until the pH reaches 9-10. The reaction temperature is controlled at 30℃. After the addition is completed, stirring is continued for 2 hours, and then the temperature is lowered to -5℃ for aging treatment for 8 hours.

[0067] (3) After step (2) is completed, the reaction solution is filtered, the filter cake is washed with distilled water, and then the filter cake is dried at 120°C for 6 hours and then calcined at 600°C for 6 hours. After grinding, it is sieved through a 30-mesh sieve to obtain the composite carrier TiO2-SiO2 (n(Ti) / n(Si)=1:1), hereinafter referred to as TS-1.

[0068] Example 2

[0069] This embodiment provides a method for preparing a solid acid catalyst (16% Zr / TS-1), including the following steps:

[0070] (S1) Dissolve 5.59g of zirconium oxynitrate dihydrate in 30.0g of distilled water to obtain an aqueous solution of zirconium oxynitrate;

[0071] (S2) Under stirring (500 rpm), 10.0 g of TS-1 prepared in Example 1 was added to an aqueous solution of zirconium oxynitrate. The mixture was impregnated for 12 h, most of the water was removed by rotary evaporation, dried at 110 °C for 4 h, and calcined at 750 °C for 5 h to obtain a solid acid catalyst: 16% Zr / TS-1 (where 16% Zr refers to the zirconium loading being 16% of the mass of the solid acid catalyst). Its EDS chromatogram is shown below. Figure 1 As shown.

[0072] Example 3

[0073] This embodiment provides a method for preparing a solid acid catalyst (12% Zr / TS-1). Compared with Example 2, this embodiment only changes the zirconium loading, while all other aspects are the same as Example 2.

[0074] Example 4

[0075] This embodiment provides a method for preparing a solid acid catalyst (14% Zr / TS-1). Compared with Example 2, this embodiment only changes the zirconium loading, while all other aspects are the same as Example 2.

[0076] Example 5

[0077] This embodiment provides a method for preparing a solid acid catalyst (18% Zr / TS-1). Compared with Example 2, this embodiment only changes the zirconium loading, while all other aspects are the same as Example 2.

[0078] Example 6

[0079] This embodiment provides a method for preparing a solid acid catalyst (12% Ce / TS-1), comprising the following steps:

[0080] (S1) Dissolve 3.78g of cerium tetranitrate in 30.0g of distilled water to obtain an aqueous solution of cerium tetranitrate;

[0081] (S2) Add 10.0g of TS-1 prepared in Example 1 under stirring (500rpm), impregnate for 12h, remove most of the water by rotary evaporation, dry at 110℃ for 4h, and calcine at 750℃ for 5h to obtain solid acid catalyst: 12%Ce / TS-1 (wherein, 12%Ce refers to the cerium loading being 12% of the mass of the solid acid catalyst).

[0082] Example 7

[0083] This embodiment provides a method for preparing a solid acid catalyst (14% Sn / TS-1), including the following steps:

[0084] (S1) Dissolve 3.57g of tin tetrachloride in 30.0g of distilled water to obtain an aqueous solution of tin tetrachloride;

[0085] (S2) Add 10.0g of TS-1 prepared in Example 1 under stirring (500rpm), impregnate for 12h, remove most of the water by rotary evaporation, dry at 110℃ for 4h, and calcine at 750℃ for 5h to obtain solid acid catalyst: 14%Sn / TS-1 (wherein, 14%Sn means that the tin loading is 14% of the mass of the solid acid catalyst).

[0086] Example 8

[0087] This embodiment provides a method for preparing a solid acid catalyst (18% Zn / TS-1), including the following steps:

[0088] (S1) Dissolve 9.99g of zinc nitrate hexahydrate in 35.0g of distilled water to obtain an aqueous solution of zinc nitrate;

[0089] (S2) Add 10.0g of TS-1 prepared in Example 1 under stirring (500rpm), impregnate for 12h, remove most of the water by rotary evaporation, dry at 110℃ for 4h, and calcine at 750℃ for 5h to obtain solid acid catalyst: 18%Zn / TS-1 (wherein, 18%Zn means that the zinc loading is 18% of the mass of the solid acid catalyst).

[0090] Example 9

[0091] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0092] Succinic anhydride and solid acid catalysts (12% Zr / TS-1 prepared in Example 3, 14% Zr / TS-1 prepared in Example 4, 16% Zr / TS-1 prepared in Example 2, and 18% Zr / TS-1 prepared in Example 5, respectively) were added to a reactor equipped with a stirrer, thermometer, and drying tube. The reaction temperature was 120°C, and L-menthol was added dropwise. After the addition was complete, the reaction continued. The total reaction time was 3 hours. The results are shown in Table 1.

[0093] In this embodiment, the molar ratio of succinic anhydride to L-menthol is 1.2:1, and the weight ratio of solid acid catalyst to L-menthol is 1:50.

[0094] Table 1 Summary of Product Content

[0095] 12% Zr / TS-1 1.2 98.4 0.4 14% Zr / TS-1 0.8 98.7 0.5 16% Zr / TS-1 0.3 99.1 0.6 18% Zr / TS-1 0.5 98.9 0.6

[0096] Example 10

[0097] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0098] Succinic anhydride and solid acid catalysts (16% Zr / TS-1 prepared in Example 2, 12% Ce / TS-1 prepared in Example 6, 14% Sn / TS-1 prepared in Example 7, and 18% Zn / TS-1 prepared in Example 8, respectively) were added to a reactor equipped with a stirrer, thermometer, and drying tube. The reaction temperature was 120°C, and L-menthol was added dropwise. After the addition was complete, the reaction continued. The total reaction time was 3 hours. The results are shown in Table 2.

[0099] The control group consisted of samples without added catalysts.

[0100] In this embodiment, the molar ratio of succinic anhydride to L-menthol is 1.2:1, and the weight ratio of solid acid catalyst to L-menthol is 1:50.

[0101] Table 2 Summary of Product Content

[0102] Catalyst-free 25.3 74.5 0.2 16% Zr / TS-1 0.3 99.1 0.6 12% Ce / TS-1 0.9 98.0 1.0 14% Sn / TS-1 2.3 96.0 1.5 18% Zn / TS-1 0.5 98.7 0.8

[0103] Example 11

[0104] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0105] Succinic anhydride and the solid acid catalyst 16% Zr / TS-1 prepared in Example 2 were added to a reactor equipped with a stirrer, thermometer and drying tube. The reaction temperatures were 110℃, 120℃, 130℃ and 140℃, respectively. L-menthol was added dropwise, and the reaction continued after the addition was completed. The total reaction time was 3h. The results are shown in Table 3.

[0106] In this embodiment, the molar ratio of succinic anhydride to L-menthol is 1.2:1, and the weight ratio of solid acid catalyst to L-menthol is 1:50.

[0107] Table 3 Summary of Product Content

[0108] 110℃ 14.25 85.6 0.30 120℃ 0.3 99.1 0.60 130℃ 0.3 95.6 0.80 140℃ 0.2 93.8 1.25

[0109] Example 12

[0110] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0111] Succinic anhydride and the solid acid catalyst 16% Zr / TS-1 prepared in Example 2 were added to a reactor equipped with a stirrer, thermometer and drying tube. The mixture was heated to 120°C and L-menthol was added dropwise. After the addition was complete, the reaction continued. The total reaction time was 3 hours. The results are shown in Table 4.

[0112] In this embodiment, the molar ratio of succinic anhydride to L-menthol is 1.2:1, and the weight ratio of solid acid catalyst to L-menthol is 1:50.

[0113] Table 4 Summary of Product Content

[0114] 2h 5.0 94.5 0.50 3h 0.3 99.1 0.60 4h 0.3 97.6 0.65 5h 0.2 96.4 0.84

[0115] Example 13

[0116] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0117] Succinic anhydride and the solid acid catalyst 16% Zr / TS-1 prepared in Example 2 were added to a reactor equipped with a stirrer, thermometer and drying tube. The reaction temperature was 120°C. L-menthol was added dropwise. After the addition was complete, the reaction continued. The total reaction time was 3 hours. The results are shown in Table 5.

[0118] In this embodiment, the molar ratios of succinic anhydride to L-menthol are 1:1, 1.2:1, 1.4:1, and 1.6:1, respectively, and the weight ratio of the solid acid catalyst to L-menthol is 1:50.

[0119] Table 5 Summary of Product Content

[0120] 1：1 1.6 96.4 2.00 1.2：1 0.3 99.1 0.60 1.4：1 0.2 98.7 0.51 1.6：1 0.1 98.5 0.51

[0121] Example 14

[0122] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0123] In a reactor equipped with a stirrer, thermometer, and drying tube, 88.0 g (0.88 mol) of succinic anhydride and 2.5 g of the solid acid catalyst prepared in Example 2, 16% Zr / TS-1, were added. The mixture was heated to 120 °C, and 124.8 g (0.80 mol) of L-menthol was added dropwise. After the addition was complete, the reaction was continued for 3 hours to obtain the reaction solution.

[0124] The reaction solution was cooled to 60°C, and 82.0 g of water was added dropwise. After the addition was complete, hydrolysis was continued for 1.0 h. The solution was cooled to room temperature and extracted with 120 ml of cyclohexane. The aqueous layer and the organic layer were separated.

[0125] Aqueous layer: water and succinic acid. After evaporating the water to dryness, the succinic acid (12.0g white solid) is recovered.

[0126] Organic layer: cyclohexane, L-menthol, menthyl succinate mono- and menthyl succinate di-; cyclohexane was recovered and the product was obtained by high-vacuum distillation (vacuum degree: 0.2-0.3 mmHg), successively yielding fraction one (L-menthol) and fraction two (menthyl succinate mono-), the specific results of which are shown in Table 6.

[0127] Table 6 Summary of Product Content

[0128] reaction solution content 0.29％ 2.4％ 96.7％ 0.59％ After washing with water, the reaction solution 0.30％ 0.0％ 99.1％ 0.60％ Fraction 1, 5.0g 12.0％ 88.0％ Fraction 2, 201.1g 0.0％ 99.9％ 0.1％ 10.0g inside the bottle 0.0％ 87.4％ 12.4％

[0129] Example 15

[0130] This embodiment provides a method for preparing menthyl succinate monosuccinate, comprising the following steps:

[0131] Succinic anhydride and the solid acid catalyst 16% Zr / TS-1 prepared in Example 2 were added to a reactor equipped with a stirrer, thermometer and drying tube. The reaction temperature was 120°C. L-menthol was added dropwise, and the reaction continued after the addition was completed. The total reaction time was 3 hours. The solid acid catalyst was reused 5 times. The results are shown in Table 7.

[0132] In this embodiment, the molar ratio of succinic anhydride to menthol is 1.2:1, and the weight ratio of solid acid catalyst to menthol is 1:50.

[0133] Table 7 Summary of Product Content

[0134] 1 0.3 99.1 0.60 2 0.7 98.7 0.60 3 0.8 98.6 0.55 4 1.2 98.2 0.50 5 2.6 96.8 0.48

[0135] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the interpretation of the present invention, without departing from the scope of the invention, should be within the protection scope of the present invention.

Claims

1. The application of a solid acid catalyst in the preparation of menthyl succinate, characterized in that, The preparation method of the solid acid catalyst includes the following steps: (S1) Tetrabutyl titanate solution and tetraethyl orthosilicate solution were mixed, and then ammonia water was added dropwise to react. After the reaction was completed, the mixture was aged and post-treated to obtain the composite support TiO2-SiO2. (S2) The composite support TiO2-SiO2 prepared by the metal salt solution impregnation step (S1) is subjected to evaporation, drying and calcination treatment to obtain a solid acid catalyst; The metal salt solution is selected from one of zirconium salt, cerium salt, tin salt, or zinc salt. In step (S1), the molar ratio of titanium to silicon is 1:1; Ammonia solution was added dropwise until the pH of the solution reached 9-10. During the reaction, the temperature is 25~30℃ and the time is 2~3 hours; During the aging process, the temperature is -5 to -10℃ and the time is 5 to 10 hours; In step (S2), when the metal salt is a zirconium salt, the zirconium loading is 12~18 wt%; When the metal salt is a cerium salt, the cerium loading is 12~18 wt%; When the metal salt is a tin salt, the tin loading is 14.5~20.5 wt%; When the metal salt is a zinc salt, the zinc loading is 8.5~14.5 wt%; During the roasting process, the temperature is 700~800℃ and the time is 4~5 hours; The preparation method of menthyl succinate includes the following steps: (A1) Succinic anhydride and solid acid catalyst are heated and melted, then mixed with menthol and reacted to obtain an intermediate product; (A2) After dissolving the intermediate product of step (A1), filter to recover the solid acid catalyst, heat the reaction solution and then add water to continue the reaction. After post-treatment, succinic acid monomenthol ester is obtained. In step (A1), the molar ratio of succinic anhydride to menthol is 1~1.6:1; the mass ratio of solid acid catalyst to menthol is 1~4:100; during the reaction, the temperature is 110~140℃ and the time is 2~5h. In step (A2), the temperature during the reaction is 55~60℃; The yield of menthyl succinate monosuccinate was 99.9%. The yield of menthyl succinate was 96.8% after the solid acid catalyst was reused 5 times.

2. The application of the solid acid catalyst according to claim 1 in the preparation of menthyl succinate mono-coated ester, characterized in that, In step (S1), the post-processing is as follows: after aging, the precipitated solids are sequentially filtered, washed, dried, roasted, ground, and sieved.

3. The application of the solid acid catalyst according to claim 1 in the preparation of menthyl succinate mono-coated ester, characterized in that, In step (S2), the zirconium salt is selected from either zirconium nitrate dihydrate or zirconium dichloride octahydrate; The cerium salt is selected from cerium nitrate; The tin salt is selected from tin tetrachloride; The zinc salt is selected from either zinc sulfate or zinc chloride.

4. The application of the solid acid catalyst according to claim 1 in the preparation of menthyl succinate mono-catalyst, characterized in that, In step (S2), the soaking time is 10-15 hours. The drying process is carried out at a temperature of 110℃.

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