Sulfonated modified mesoporous molecular sieve catalyst with high specific surface area, preparation method of sulfonated modified mesoporous molecular sieve catalyst and application of sulfonated modified mesoporous molecular sieve catalyst in cyclohexyl acetate synthesis reaction

Abstract

The invention relates to the field of fine chemical engineering, and discloses a sulfonation modified mesoporous molecular sieve catalyst with a high specific surface area, a preparation method of the sulfonation modified mesoporous molecular sieve catalyst and application of the sulfonation modified mesoporous molecular sieve catalyst in cyclohexyl acetate synthesis reaction. The sulfonation modified mesoporous molecular sieve catalyst with the high specific surface area is obtained by sulfonating a mesoporous molecular sieve with the high specific surface area, and the surface sulfonic acid group of the sulfonation modified mesoporous molecular sieve catalyst with the high specific surface area is 1.2-3.5 mmol / g. The sulfonation modified mesoporous molecular sieve catalyst with high specific surface area is used for a synthetic reaction of cyclohexyl acetate, and a higher esterification rate can be obtained.

Description

Technical Field

[0001] The invention relates to the field of fine chemicals, and in particular to a sulfonated modified high specific surface area mesoporous molecular sieve catalyst and a preparation method thereof, as well as application of the catalyst in a cyclohexyl acetate synthesis reaction. Background Art

[0002] Cyclohexyl acetate, also known as cyclohexyl acetate, is a colorless or slightly yellowish transparent oily liquid with a banana or apple aroma. It is an important flavor in the food industry and is often used to prepare flavors such as apples, bananas, black currants and raspberries, and is widely used in beverages, ice cream and other foods. In addition, it is also a common flavor in the daily cosmetics industry. At the same time, due to its good solubility in resins, it is often used as a solvent for coatings, paints, etc. In industry, acetic acid and cyclohexanol are commonly used as raw materials and concentrated sulfuric acid is used as a catalyst to synthesize cyclohexyl acetate. However, since cyclohexanol is a secondary alcohol, it is easily dehydrated to form cyclohexene under the action of concentrated sulfuric acid, which reduces the esterification rate. In addition, the use of concentrated sulfuric acid as a catalyst also has the disadvantages of severe equipment corrosion, complex post-treatment process, and environmental pollution. p-Toluenesulfonic acid is a common and easily available strong organic acid that can be used for esterification reactions. Compared with concentrated sulfuric acid, p-toluenesulfonic acid has the advantages of high activity, good selectivity, high product purity, high yield, no corrosion to equipment, and reduced pollution. However, p-toluenesulfonic acid is easily soluble in water, alcohol and ether, is very easy to deliquesce, and has poor water resistance, which affects its application in catalytic esterification.

[0003] In order to make up for the defects of inorganic acid esterification catalysts and organic acid esterification catalysts, in recent years, there have been many studies on new esterification catalysts such as inorganic salts, ion exchange resins, solid superacids and molecular sieves, and the esterification reaction mode has also developed from homogeneous reaction to multiphase reaction. Solid catalysts show advantages such as good stability, high selectivity, low cost and easy separation in esterification reactions. However, this type of catalyst has a slow reaction rate and a low ester yield. Cation exchange resins show advantages such as good stability, high selectivity, low cost and easy separation in esterification reactions. However, the cation exchange resin itself has poor heat resistance (generally suitable for esterification reactions at temperatures below 150°C), small specific surface area and pore volume, and the cation exchange resin is easy to swell. As an esterification catalyst, the reaction activity is poor and the ester yield is low. Compared with resin catalysts, hydrogen-type zeolite molecular sieves have certain pore structures and surface acidity, which are suitable for catalyzing the esterification reaction of small molecules. However, the pore size of zeolite molecular sieve is relatively small (0.5-0.7nm), which may inhibit the diffusion of macromolecular products during the reaction; and the number of acidic sites on the surface of zeolite molecular sieve is relatively small, and the efficiency of catalytic esterification reaction is low. Therefore, it is unrealistic to directly apply hydrogen-type zeolite molecular sieve materials to the synthesis reaction of cyclohexyl acetate. With the increasing demand for cyclohexyl acetate, the prospect of synthesizing cyclohexyl acetate by green and environmentally friendly process is broad. For researchers, developing excellent performance catalysts for cyclohexyl acetate synthesis reaction, improving reaction efficiency and inhibiting the formation of by-products are important work directions in the future. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of excessive side reactions and serious environmental pollution of the inorganic acid catalyst used in the cyclohexyl acetate production process in the prior art, as well as the problems of poor catalytic activity and low esterification rate of the zeolite molecular sieve catalyst and the acidic cation exchange resin catalyst, and to provide a sulfonated modified high specific surface area mesoporous molecular sieve catalyst and a preparation method thereof and application in the cyclohexyl acetate synthesis reaction. The present invention uses the sulfonated modified high specific surface area mesoporous molecular sieve catalyst in the synthesis reaction of cyclohexyl acetate to obtain a higher esterification rate.

[0005] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a sulfonated modified high specific surface area mesoporous molecular sieve catalyst, wherein the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is obtained by sulfonating a high specific surface area mesoporous molecular sieve, and the surface sulfonic acid group of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is 1.2-3.5 mmol / g.

[0006] The second aspect of the present invention provides a method for preparing a sulfonated modified high specific surface area mesoporous molecular sieve catalyst, wherein the preparation method comprises: contacting the high specific surface area mesoporous molecular sieve with a halosulfonic acid for sulfonation treatment to obtain a sulfonated modified high specific surface area mesoporous molecular sieve catalyst;

[0007] Wherein, the weight ratio of the high specific surface area mesoporous molecular sieve to the halosulfonic acid is 1:(0.2-1.5).

[0008] The third aspect of the present invention provides a sulfonated modified high specific surface area mesoporous molecular sieve catalyst prepared by the aforementioned preparation method.

[0009] A fourth aspect of the present invention provides an application of the aforementioned sulfonated modified high specific surface area mesoporous molecular sieve catalyst in the synthesis reaction of cyclohexyl acetate.

[0010] Through the above technical solution, the technical solution of the present invention has the following advantages:

[0011] (1) The high specific surface area mesoporous molecular sieve provided by the present invention is an all-silicon ordered mesoporous molecular sieve material with a stable structure and good high temperature resistance. After sulfonation modification, it is used in esterification reaction, and the mesoporous channel structure is conducive to the diffusion of raw material and product molecules.

[0012] (2) The sulfonated modified high specific surface area mesoporous molecular sieve catalyst provided by the present invention has uniformly dispersed surface active components, strong esterification catalytic ability and high esterification rate.

[0013] (3) The raw materials of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst provided by the present invention are easy to obtain, the preparation method is simple, the conditions are easy to control, and the product has good reproducibility.

[0014] (4) When the sulfonated modified high specific surface area mesoporous molecular sieve catalyst provided by the present invention is used in the synthesis reaction of cyclohexyl acetate, the process conditions are mild and the requirements for the reaction device are not high.

[0015] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is the XRD spectrum of the high specific surface area mesoporous molecular sieve A prepared in Example 1;

[0017] Figure 2 is a TEM image of the high specific surface area mesoporous molecular sieve A prepared in Example 1;

[0018] Figure 3 This is the XRD spectrum of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst A prepared in Example 1. DETAILED DESCRIPTION

[0019] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0020] As mentioned above, the first invention of the present invention provides a sulfonated modified high specific surface area mesoporous molecular sieve catalyst, wherein the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is obtained by sulfonating a high specific surface area mesoporous molecular sieve, and the surface sulfonic acid group of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is 1.2-3.5 mmol / g.

[0021] The inventor of the present invention has found that: in the prior art, the esterification catalysts used to produce cyclohexyl acetate are divided into two categories: homogeneous and heterogeneous. Among them, homogeneous catalysts mainly include inorganic acid solutions and organic acids, and heterogeneous catalysts mainly include solid acids and cation exchange resins. The advantages of homogeneous catalysts are low price and good catalytic activity, but they are gradually eliminated due to defects such as difficulty in separating products from catalysts, more side reactions, and easy corrosion of equipment. Although solid acid esterification catalysts solve the problems of difficult product separation and serious equipment corrosion, they are rarely used in industrial production due to shortcomings such as poor catalytic activity, high reaction temperature, and low product selectivity. Compared with the above catalysts, resin catalysts have the advantages of high selectivity, low cost and easy separation, but the esterification rate is low in the cyclohexyl acetate synthesis reaction process, and the high temperature resistance is also poor. Resin is an organic polymer material, which is easy to swell in organic solvents, easy to deform or even decompose in high temperature environments, which is the main reason for the poor temperature resistance of resin catalysts.

[0022] In recent years, acidic zeolite molecular sieve catalysts have attracted extensive attention from researchers due to their stable structure and the advantages of active centers not easy to lose, and are often used as catalysts for esterification reactions. However, the pore size of zeolite molecular sieves is in the micropore range and the pore size is small. If the reactant molecules, intermediates or target product molecules involved in the reaction are large in size, catalysts with smaller pore sizes are not conducive to diffusion, which leads to a decrease in catalytic performance. Therefore, according to the specific circumstances of the esterification reaction, catalysts with larger pore sizes should be used when larger molecules are involved in the reaction. All-silicon mesoporous molecular sieve materials have structural advantages of large specific surface area and large pore volume and high temperature resistance. Compared with zeolite molecular sieves, the pore structure of high specific surface area mesoporous molecular sieves is more suitable for esterification reactions involving large molecules. However, the surface acidity of all-silicon mesoporous molecular sieve materials themselves is weak, and the catalytic performance in esterification reactions is poor. If the above problems are to be solved, it is necessary to increase the number and strength of acid centers on the surface of mesoporous molecular sieves.

[0023] The inventors of the present invention have found in the process of developing esterification catalysts that if a high specific surface area mesoporous molecular sieve is appropriately sulfonated, the obtained sulfonated modified high specific surface area mesoporous molecular sieve catalyst can be used for the synthesis reaction of cyclohexyl acetate. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst has the characteristics of high catalytic activity, simple preparation, small amount, etc., and this catalyst belongs to an inorganic structure, not only will not swell and deform in an organic solvent, but also has good temperature resistance. The reacted catalyst is insoluble in an organic system, is easily separated from the product, is simple to post-process, has good reusability, is an environmentally friendly catalyst, and has good application prospects.

[0024] According to the present invention, preferably, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst are 1.6-3.2 mmol / g, more preferably 2.0-2.8 mmol / g.

[0025] According to the present invention, the high specific surface area mesoporous molecular sieve is a mesoporous molecular sieve with a silicon dioxide content of 100%.

[0026] According to the present invention, the specific surface area of ​​the high specific surface area mesoporous molecular sieve is 800-1600m 2 / g, an average pore size of 2-5nm, and a pore volume of 0.7-1.8mL / g; preferably, the high specific surface area mesoporous molecular sieve has a specific surface area of ​​900-1400m 2 / g, the average pore size is 2-4nm, and the pore volume is 0.9-1.6mL / g. In the present invention, the above-mentioned specific high specific surface area mesoporous molecular sieve structural parameters are adopted to enable the prepared catalyst to have better catalytic activity and higher esterification rate when used in acetic acid esterification reaction.

[0027] According to the present invention, the method for preparing the high specific surface area mesoporous molecular sieve comprises:

[0028] (1) mixing a template agent, an auxiliary template agent and deionized water to obtain a mixture; wherein the template agent is a quaternary ammonium cation template agent, and the auxiliary template agent has a general formula shown in formula (b);

[0029] [NR 1 R 2 R 3 R 4 ] + OH - , formula (b);

[0030] Among them, R 1 , R 2 , R 3 and R 4 The same or different, each is a C1-C4 straight chain or branched alkyl group;

[0031] (2) adding a low-carbon alcohol and a silicon source dropwise into the mixture to contact and react, and then subjecting the mixture to crystallization, filtration, separation and washing to obtain a raw powder of a high specific surface area mesoporous molecular sieve;

[0032] (3) The high specific surface area mesoporous molecular sieve raw powder is mixed with anhydrous ethanol and concentrated hydrochloric acid, and then filtered, washed, dried and the template agent is removed to obtain a high specific surface area mesoporous molecular sieve.

[0033] According to the present invention, preferably, the auxiliary template agent is selected from one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetraisopropylammonium hydroxide.

[0034] According to the present invention, preferably, the template has the general formula shown in formula (a);

[0035] [NR 1 R 2 R 3 R 4 ] + X - ; Formula (a);

[0036] Among them, R 1 Represents C 12 -C 30 A straight chain or branched alkyl group;

[0037] R 2 , R 3 and R 4 The same or different, each is a C1-C4 straight chain or branched alkyl group;

[0038] X represents a halogen element, and is preferably one or more selected from fluorine, chlorine and bromine.

[0039] According to the present invention, more preferably, the template is selected from one or more of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride and octadecyltrimethylammonium chloride.

[0040] According to the present invention, the low-carbon alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol, preferably one or more of methanol, ethanol, isopropanol and isobutanol.

[0041] According to the present invention, the silicon source is an organic silicon-containing compound and / or an inorganic silicon-containing compound, preferably one or more of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate, silica sol and sodium metasilicate, more preferably methyl orthosilicate and / or ethyl orthosilicate.

[0042] According to the present invention, the weight ratio of the template, the auxiliary template, the low-carbon alcohol, the silicon source and the deionized water is 1: (0.1-1.2): (0.1-4.0): (0.5-6.0): (1-20), preferably 1: (0.2-0.8): (0.2-2.0): (1.0-4.0): (2-10).

[0043] According to the present invention, the contact reaction conditions may be a temperature of 10-70°C, preferably 20-50°C, and a time of 0.5-10h, preferably 1-4h. Preferably, in order to speed up the contact reaction, the contact may be carried out under stirring.

[0044] According to the present invention, the crystallization conditions may be a temperature of 10-120°C, preferably 20-100°C; a time of 2-48h, preferably 3-24h. The crystallization treatment may be performed under static or stirring conditions. Preferably, in order to make the mesoporous structure grow uniformly during the crystallization process, the crystallization may be performed under stirring conditions.

[0045] According to the present invention, there are no special requirements for the solid-liquid two-phase separation process, and it can be a separation method known in the art, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the separation process specifically includes: using a suction bottle, vacuuming the bottom side of the funnel or filtering with a centrifugal filter.

[0046] According to the present invention, there is no special requirement for the method of washing the solid product. For example, the solid product can be washed with deionized water, the volume ratio of deionized water to the solid product can be 5-20, and the number of washing times can be 2-8 times.

[0047] The drying conditions may be a temperature of 70-130° C., preferably 90-110° C., and a time of 2-30 h, preferably 5-20 h.

[0048] The method for removing the template agent treatment can be: the raw powder of the high specific surface area mesoporous molecular sieve is mixed with anhydrous ethanol and concentrated hydrochloric acid, filtered, washed and dried, and the treated solid product is refluxed in an organic extract, the extraction temperature can be 60-90° C., and the extraction time can be 8-36 hours. The organic extract in the present invention is preferably one or more of acidified methanol, acidified ethanol and tetrahydrofuran.

[0049] According to the present invention, the specific surface area of ​​the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is 500-1200m 2 / g, pore volume 0.7-1.4cm 3 / g, and an average pore size of 1.5-2.6nm; preferably, the specific surface area of ​​the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is 700-1100m 2 / g, pore volume is 1.0-1.3cm 3 / g, and the average pore size is 2.0-2.5nm.

[0050] The second aspect of the present invention provides a method for preparing a sulfonated modified high specific surface area mesoporous molecular sieve catalyst, wherein the preparation method comprises: contacting the high specific surface area mesoporous molecular sieve with a halosulfonic acid for sulfonation treatment to obtain a sulfonated modified high specific surface area mesoporous molecular sieve catalyst;

[0051] Wherein, the weight ratio of the high specific surface area mesoporous molecular sieve to the halosulfonic acid is 1:(0.2-1.5).

[0052] According to the present invention, preferably, the weight ratio of the high specific surface area mesoporous molecular sieve to the halosulfonic acid is 1:(0.4-0.8).

[0053] According to the present invention, the halosulfonic acid is selected from one or more of fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid and iodosulfonic acid, preferably chlorosulfonic acid; in the present invention, the advantage of using halosulfonic acid is that the halosulfonic acid can be riveted to the surface of the silica gel material in the form of chemical bonds during the modification process, the properties are relatively stable, and the utilization rate of the active groups of the catalyst is high.

[0054] According to the present invention, the specific surface area of ​​the high specific surface area mesoporous molecular sieve is 800-1600m 2 / g, an average pore size of 2-5nm, and a pore volume of 0.7-1.8mL / g; preferably, the high specific surface area mesoporous molecular sieve has a specific surface area of ​​900-1400m 2 / g, the average pore diameter is 2-4nm, and the pore volume is 0.9-1.6mL / g.

[0055] According to the present invention, in the method for preparing the sulfonated modified high specific surface area mesoporous molecular sieve catalyst, the method for preparing the high specific surface area mesoporous molecular sieve is the same as described above and will not be repeated herein.

[0056] According to the present invention, the contact conditions include: the reaction temperature can be 30-80°C, preferably 40-60°C; the reaction time can be 0.2-8 hours, preferably 0.5-4 hours. Preferably, in order to achieve better reaction effect, the high specific surface area mesoporous molecular sieve can be quickly stirred during the contact reaction with the halosulfonic acid to improve the reaction efficiency.

[0057] According to the present invention, a high specific surface area mesoporous molecular sieve is contacted with a halosulfonic acid for sulfonation treatment, and the gas generated in the reaction is absorbed by an alkaline aqueous solution.

[0058] According to the present invention, the alkaline aqueous solution can be a NaOH aqueous solution, a KOH aqueous solution, a NaHCO3 aqueous solution or a Na2CO3 aqueous solution, preferably a NaOH aqueous solution or a KOH aqueous solution.

[0059] The third aspect of the present invention provides a sulfonated modified high specific surface area mesoporous molecular sieve catalyst prepared by the aforementioned preparation method.

[0060] A fourth aspect of the present invention provides an application of the aforementioned sulfonated modified high specific surface area mesoporous molecular sieve catalyst in the synthesis reaction of cyclohexyl acetate.

[0061] According to the present invention, the application comprises: in the presence of a water-carrying agent cyclohexane, contacting the sulfonated modified high specific surface area mesoporous molecular sieve catalyst, acetic acid and cyclohexanol to react.

[0062] According to the present invention, the contact reaction conditions include: reaction temperature of 70-130° C., reaction time of 0.5-8 h; preferably, reaction temperature of 80-110° C., reaction time of 1-3 h.

[0063] And / or, the weight ratio of the acetic acid, the cyclohexanol, the sulfonated modified high specific surface area mesoporous molecular sieve catalyst and the water-carrying cyclohexane is 1:(1-10):(0.01-0.1):(0.5-6), preferably 1:(2-4):(0.02-0.04):(1-3).

[0064] The present invention will be described in detail below through examples.

[0065] (1) The small-angle XRD test of the samples was carried out on a D8 ADVANCE high-power rotating target X-ray diffractometer produced by BRUKER AXS, Germany, with a scanning range of 0.5-10°.

[0066] (2) The pore structure parameter analysis of the samples was carried out on an ASAP2020-M+C adsorption instrument purchased from Micromeritics, Inc., USA. The samples were vacuum degassed at 350°C for 4 hours before measurement. The specific surface area of ​​the samples was calculated using the BET method, and the pore volume was calculated using the BJH model.

[0067] (3) Transmission electron microscopy (TEM) images of the samples were obtained using a Tecnai F20 high-resolution transmission electron microscope produced by FEI Philips of the Netherlands.

[0068] (4) The elemental analysis of the samples was carried out on an Eagle III energy dispersive X-ray fluorescence spectrometer produced by EDAX, USA. The density of sulfonic acid groups on the catalyst surface was calculated by the S content on the modified ultra-macroporous silica catalyst.

[0069] (5) The drying oven was manufactured by Shanghai Yiheng Scientific Instrument Co., Ltd., model DHG-9030A.

[0070] (6) The reagents used in the examples and comparative examples were purchased from Sinopharm Chemical Reagent Co., Ltd. and were of analytical purity.

[0071] Example 1

[0072] (1) Preparation of high specific surface area mesoporous molecular sieves

[0073] At 25°C, add 50g hexadecyltrimethylammonium bromide, 12g tetramethylammonium hydroxide and 200g deionized water to a 1000ml round-bottom flask, mix and stir for 10 minutes to dissolve the template. 75g tetramethyl orthosilicate and 11g methanol are fully mixed and slowly added to the flask, and the mixed solution is stirred during the addition. After the addition is completed, stir at 25°C for 10 hours for crystallization. After the crystallization is completed, the white solid product is filtered to obtain the white solid product, which is washed with deionized water 8 times and dried in air at 100°C for 10 hours to obtain the high specific surface area mesoporous molecular sieve powder. The high specific surface area mesoporous molecular sieve powder is mixed with 200ml anhydrous methanol and 10ml concentrated hydrochloric acid, and refluxed at 80°C for 12 hours. Then filter, wash the solid product with anhydrous methanol and vacuum dry at 120°C for 3 hours to obtain a high specific surface area mesoporous molecular sieve A.

[0074] The specific surface area of ​​high specific surface area mesoporous molecular sieve A is 1237m 2 / g, pore volume 1.5cm 3 / g, and the average pore size is 2.8nm.

[0075] Figure 1 This is the XRD spectrum of high specific surface area mesoporous molecular sieve A. The spectrum shows that the sample has a very strong diffraction peak near 2θ=2.4°, and two weaker peaks appear near 2θ=4.1° and 4.7°. These three clearly identifiable diffraction peaks correspond to the (100), (110) and (200) crystal planes, respectively, indicating that the sample has a typical two-dimensional hexagonal mesoporous structure and a high degree of regularity of the long-range ordered structure.

[0076] Figure 2 This is a TEM image of high specific surface area mesoporous molecular sieve A. It can be seen that the mesoporous structure of the sample is regularly arranged in a hexagonal structure, and the pore spacing is between 2-4nm.

[0077] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0078] Under the temperature condition of 50°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve A to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 12 grams of chlorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the NaOH aqueous solution. Under the stirring condition of a stirring rate of 600 rpm, add chlorosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the NaOH aqueous solution. After all the chlorosulfonic acid has been added, continue stirring for 2 hours. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst A.

[0079] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst A was 1004 m 2 / g, pore volume 1.2cm 3 / g, and the average pore size is 2.3nm.

[0080] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst A are 2.5 mmol / g.

[0081] Figure 3 This is the XRD spectrum of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst A. Figure 3 The spectrum shows that the catalyst has obvious diffraction signals at 2θ=2.7°, 4.4° and 5.0°. Figure 1 Compared with the XRD spectrum of medium and high specific surface area mesoporous molecular sieve A, Figure 3 Each diffraction signal in the sulfonation treatment has moved toward the high angle direction, and the intensity of the diffraction peak has decreased significantly. This shows that after sulfonation, the mesoporous molecular sieve still maintains a relatively regular basic mesoporous channel structure, but the pore size becomes narrower and the regularity of the channel decreases to a certain extent. This is because some sulfonic acid groups enter the mesoporous molecular sieve channel during the sulfonation process, resulting in a narrowing of the apparent pore size, a decrease in pore volume, and a decrease in the regularity of the channel.

[0082] (3) Catalyst reaction performance evaluation

[0083] 10g acetic acid, 26g cyclohexanol, 0.3g sulfonated modified high specific surface area mesoporous molecular sieve catalyst A and 15g water-carrying cyclohexane were added to a 200mL four-necked flask, and a thermometer, water separator and condenser were installed. The mixture was heated to reflux for 2h, cooled to room temperature and allowed to stand for 3h. After the solid catalyst was settled, the organic layer was transferred and the fraction of 168-172°C was collected by distillation to obtain colorless, transparent and fragrant cyclohexyl acetate. The acid value before and after the reaction was determined according to GB / T1668-1995, and the esterification rate of the esterification reaction was calculated according to the following formula: esterification rate = (1-acid value after reaction / acid value before reaction) × 100%.

[0084] Catalyst A reaction evaluation results: esterification rate was 99.2%.

[0085] Example 2

[0086] (1) Preparation of high specific surface area mesoporous molecular sieves

[0087] At 50°C, add 50g of octadecyltrimethylammonium chloride, 10g of tetramethylammonium hydroxide and 150g of deionized water to a 1000ml round-bottom flask, mix and stir for 20 minutes to dissolve the template. 50g of tetraethyl orthosilicate and 10g of ethanol are fully mixed and slowly added to the flask, and the mixed solution is stirred during the addition. After the addition is completed, the mixture is transferred to a stainless steel synthesis reactor equipped with a polytetrafluoroethylene liner and stirred and crystallized at 100°C for 3 hours. After the crystallization is completed, the synthesis reactor is cooled to room temperature, and a white solid product is obtained by suction filtration. It is washed with deionized water 6 times and dried in air at 110°C for 5 hours to obtain a high specific surface area mesoporous molecular sieve raw powder. The high specific surface area mesoporous molecular sieve raw powder is mixed with 150ml of anhydrous ethanol and 8ml of concentrated hydrochloric acid, and refluxed and extracted at 70°C for 24 hours. Then, after filtration, the solid product is washed with anhydrous ethanol and vacuum dried at 110°C for 12 hours to obtain a high specific surface area mesoporous molecular sieve B.

[0088] The specific surface area of ​​high specific surface area mesoporous molecular sieve B is 1142m 2 / g, pore volume 1.6cm 3 / g, and the average pore size is 3.2nm.

[0089] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0090] Under the temperature condition of 60℃, add 20g of the above-mentioned high specific surface area mesoporous molecular sieve B to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 16g of chlorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under the stirring condition of a stirring rate of 500 rpm, add chlorosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the chlorosulfonic acid has been added, continue stirring for 4.0h. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst B.

[0091] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst B was 927 m 2 / g, pore volume 1.3cm 3 / g, and the average pore size is 2.5nm.

[0092] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst B are 2.8 mmol / g.

[0093] (3) Catalyst reaction performance evaluation

[0094] The esterification performance of catalyst B was tested according to the method of step (3) in Example 1. The esterification rate was 99.0%.

[0095] Example 3

[0096] (1) Preparation of high specific surface area mesoporous molecular sieves

[0097] At 20°C, add 50g dodecyltrimethylammonium chloride, 40g tetrapropylammonium hydroxide and 500g deionized water to a 1000ml round-bottom flask, mix and stir for 20 minutes to dissolve the template. After fully mixing 200g tetramethyl orthosilicate and 100g isopropanol, slowly drop them into the flask, and continue to stir the mixed solution during the dropwise addition. After the dropwise addition is completed, stir and crystallize at 20°C for 24 hours. After the crystallization is completed, cool the synthesis reactor to room temperature, filter and obtain a white solid product, wash it with deionized water 4 times, and dry it in air at 90°C for 20 hours to obtain a high specific surface area mesoporous molecular sieve raw powder. The high specific surface area mesoporous molecular sieve raw powder is mixed with 400ml tetrahydrofuran and refluxed at 90°C for 8 hours. Then filter, wash the solid product with tetrahydrofuran and vacuum dry it at 130°C for 8 hours to obtain a high specific surface area mesoporous molecular sieve C.

[0098] The specific surface area of ​​high specific surface area mesoporous molecular sieve C is 1197m 2 / g, pore volume 1.4cm 3 / g, and the average pore size is 2.7nm.

[0099] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0100] At 40°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 8 grams of chlorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under stirring conditions at a stirring rate of 800 rpm, add chlorosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the chlorosulfonic acid has been added, continue stirring for 0.5h. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst C.

[0101] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst C was 986 m 2 / g, pore volume 1.0cm 3 / g, and the average pore size is 2.0nm.

[0102] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst C are 2.0 mmol / g.

[0103] (3) Catalyst reaction performance evaluation

[0104] The esterification performance of catalyst C was tested according to the method of step (3) in Example 1. The esterification rate was 98.8%.

[0105] Example 4

[0106] A high specific surface area mesoporous molecular sieve A was prepared according to the method of step (1) in Example 1.

[0107] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0108] At 40°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve A to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 12 grams of bromosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the NaOH aqueous solution. Under stirring conditions at a stirring rate of 700 rpm, add bromosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the NaOH aqueous solution. After all the bromosulfonic acid has been added, continue stirring for 2 hours. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D.

[0109] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst D was 1100 m 2 / g, pore volume 1.3cm 3 / g, and the average pore size is 2.5nm.

[0110] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D are 1.8 mmol / g.

[0111] The catalytic performance of Catalyst D was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 97.5%.

[0112] Example 5

[0113] The high specific surface area mesoporous molecular sieve B was prepared according to the method of step (1) in Example 2.

[0114] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0115] Under the temperature condition of 80℃, add 20g of the above-mentioned high specific surface area mesoporous molecular sieve B to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 30g of bromosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under the stirring condition of a stirring rate of 400 rpm, add bromosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the bromosulfonic acid has been added dropwise, continue stirring for 4h. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst E.

[0116] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst E was 794 m 2 / g, pore volume 1.1cm 3 / g, and the average pore size is 2.3nm.

[0117] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst E are 3.0 mmol / g.

[0118] The catalytic performance of Catalyst E was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 96.1%.

[0119] Example 6

[0120] A high specific surface area mesoporous molecular sieve A was prepared according to the method of step (1) in Example 1.

[0121] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0122] At 30°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve A to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 4 grams of fluorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under stirring conditions at a stirring rate of 300 rpm, add fluorosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the fluorosulfonic acid has been added, continue stirring for 4 hours. Take out the solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst F.

[0123] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst F was 1172 m 2 / g, pore volume 1.4cm 3 / g, and the average pore size is 2.6nm.

[0124] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst F are 1.2 mmol / g.

[0125] The catalytic performance of Catalyst F was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 95.7%.

[0126] Example 7

[0127] The high specific surface area mesoporous molecular sieve B was prepared according to the method of step (1) in Example 2.

[0128] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0129] Under the temperature condition of 80℃, add 20g of the above-mentioned high specific surface area mesoporous molecular sieve B to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 21g of chlorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under the stirring condition of a stirring rate of 400 rpm, add bromosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the bromosulfonic acid has been added, continue stirring for 4h. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst G.

[0130] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst G was 548 m 2 / g, pore volume 0.7cm 3 / g, and the average pore size is 1.5nm.

[0131] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst G are 3.5 mmol / g.

[0132] The catalytic performance of Catalyst E was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 95.4%.

[0133] Comparative Example 1

[0134] The high specific surface area mesoporous molecular sieve B was prepared according to the method of step (1) in Example 2.

[0135] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0136] At 100°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve B to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 60 grams of bromosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under stirring conditions at a stirring rate of 600 rpm, add bromosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the bromosulfonic acid has been added, continue stirring for 4 hours. Take out the white solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D1.

[0137] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst D1 was 407 m 2 / g, pore volume 0.5cm 3 / g, and the average pore size is 1.1nm.

[0138] In addition, the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D1 are 4.9 mmol / g.

[0139] The catalytic performance of catalyst D1 was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 89.4%.

[0140] Comparative Example 2

[0141] A high specific surface area mesoporous molecular sieve A was prepared according to the method of step (1) in Example 1.

[0142] (2) Preparation of sulfonated high specific surface area mesoporous molecular sieve catalyst

[0143] At 10°C, add 20 grams of the above-mentioned high specific surface area mesoporous molecular sieve A to a three-necked flask equipped with a constant pressure funnel and an exhaust gas outlet pipe, and install a mechanical stirring device. Add 1.5 grams of fluorosulfonic acid to the constant pressure funnel, and connect the exhaust gas outlet pipe to the KOH aqueous solution. Under stirring conditions at a stirring rate of 200 rpm, add fluorosulfonic acid dropwise to the three-necked flask, and the acidic gas generated during the reaction is absorbed by the KOH aqueous solution. After all the fluorosulfonic acid has been added, continue stirring for 4 hours. Take out the solid in the three-necked flask, which is the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D2.

[0144] The results showed that the specific surface area of ​​the prepared sulfonated modified high specific surface area mesoporous molecular sieve catalyst D2 was 1203 m 2 / g, pore volume 1.5cm 3 / g, and the average pore size is 2.7nm.

[0145] In addition, the surface sulfonic acid group of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst D2 is 0.5 mmol / g.

[0146] The catalytic performance of catalyst D2 was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 75.1%.

[0147] Comparative Example 3

[0148] Step (1) in Example 1 was cancelled, and the high specific surface area mesoporous molecular sieve A in step (2) in Example 1 was replaced with commercially available silica (purchased from Qingdao Hailang Silica Gel Desiccant Factory, with a specific surface area of ​​329 m 2 / g, pore volume of 0.4ml / g, average pore diameter of 15nm, average particle diameter of 1.5mm), to obtain catalyst D3.

[0149] The results showed that the specific surface area of ​​the prepared sulfonated modified catalyst D3 was 241 m 2 / g, pore volume 0.3cm 3 / g, and the average pore size is 13nm.

[0150] In addition, the surface sulfonic acid group of the sulfonated modified catalyst D3 was 1.0 mmol / g.

[0151] The catalytic performance of catalyst D3 was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 88.6%.

[0152] Comparative Example 4

[0153] A high specific surface area mesoporous molecular sieve A was prepared in the same manner as step (1) in Example 1, except that step (2) in Example 1 was omitted.

[0154] The catalytic performance of the high specific surface area mesoporous molecular sieve A was tested according to the esterification reaction performance evaluation method of step (3) in Example 1. The esterification rate was 12.4%.

[0155] Comparative Example 5

[0156] A high specific surface area mesoporous molecular sieve was prepared in the same manner as step (1) in Example 1;

[0157] The sulfonated modified high specific surface area mesoporous molecular sieve catalyst D5 was prepared in the same manner as step (2) in Example 1, except that "12 g chlorosulfonic acid" was replaced by "12 g concentrated hydrochloric acid" to obtain the modified high specific surface area mesoporous molecular sieve catalyst D5.

[0158] The specific surface area of ​​the modified high specific surface area mesoporous molecular sieve catalyst D5 is 1127m 2 / g, pore volume 1.4cm 3 / g, and the average pore size is 2.7nm.

[0159] In addition, the surface sulfonic acid group of the modified high specific surface area mesoporous molecular sieve catalyst D5 is 0 mmol / g.

[0160] The catalytic performance of catalyst D5 was tested using the same catalyst reaction performance evaluation method as step (3) in Example 1.

[0161] Catalyst D5 reaction evaluation results: esterification rate was 62.3%.

[0162] It can be seen from the above results that the sulfonated modified high specific surface area mesoporous molecular sieve catalyst provided by the present invention can directly convert acetic acid and cyclohexanol into cyclohexyl acetate, and obtain a higher esterification rate of cyclohexyl acetate.

[0163] In Comparative Example 1, the amount of halosulfonic acid used in the preparation process of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is too high, the sulfonic acid groups on the surface of the prepared catalyst are aggregated and dispersed unevenly on the high specific surface area mesoporous molecular sieve. As a result, some active centers cannot effectively play a catalytic role during the reaction, resulting in a low esterification rate of cyclohexyl acetate.

[0164] In Comparative Example 2, the amount of halosulfonic acid used in the preparation process of the sulfonation-modified high specific surface area mesoporous molecular sieve catalyst is too low, resulting in poor effect of the sulfonation process. The number of sulfonic acid groups on the surface of the prepared catalyst is relatively small. The same weight of catalyst active sites are insufficient during the reaction process, resulting in a low esterification rate of cyclohexyl acetate.

[0165] In Comparative Example 3, the high specific surface area mesoporous molecular sieve specifically defined in the present invention was not used, but commercial silica was used. Since the commercial silica had an uneven pore structure, a small specific surface area, and a small pore volume, and the sulfonic acid groups were unevenly dispersed on the surface of the commercial silica, the esterification rate of cyclohexyl acetate was low.

[0166] In Comparative Example 4, the synthesis reaction of cyclohexyl acetate was catalyzed by using unmodified high specific surface area mesoporous molecular sieve A as a catalyst. Since the surface acid sites of the high specific surface area mesoporous molecular sieve material are extremely weak, the esterification reaction cannot be effectively catalyzed, resulting in an extremely low esterification rate of cyclohexyl acetate.

[0167] In Comparative Example 5, halosulfonic acid was not used as a modification agent, but concentrated hydrochloric acid was used to acidify the high specific surface area mesoporous molecular sieve. Since the modification effect of concentrated hydrochloric acid was poor, the esterification rate of cyclohexyl acetate was low.

[0168] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A sulfonated modified high specific surface area mesoporous molecular sieve catalyst, It is characterized in that The sulfonated modified high specific surface area mesoporous molecular sieve catalyst is obtained by sulfonating the high specific surface area mesoporous molecular sieve, and the surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst are 1.2-3.5 mmol / g.

2. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to claim 1, in, The surface sulfonic acid groups of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst are 1.6-3.2 mmol / g.

3. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to claim 1 or 2, in, The specific surface area of ​​the high specific surface area mesoporous molecular sieve is 800-1600m 2 / g, average pore diameter is 2-5nm, pore volume is 0.7-1.8mL / g; Preferably, the high specific surface area mesoporous molecular sieve has a specific surface area of ​​900-1400 m 2 / g, the average pore diameter is 2-4nm, and the pore volume is 0.9-1.6mL / g.

4. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to any one of claims 1 to 3, in, The preparation method of the high specific surface area mesoporous molecular sieve comprises: (1) mixing a template agent, an auxiliary template agent and deionized water to obtain a mixture; wherein the template agent is a quaternary ammonium cationic template agent, and the auxiliary template agent has a general formula shown in formula (b); [NR 1 R 2 R 3 R 4 ] + OH - , formula (b); Among them, R 1 , R 2 , R 3 and R 4 Same or different, each is C 1 -C 4 A straight chain or branched alkyl group; (2) adding a low-carbon alcohol and a silicon source dropwise into the mixture to contact and react, and then subjecting the mixture to crystallization, filtration, separation and washing to obtain a raw powder of a high specific surface area mesoporous molecular sieve; (3) The high specific surface area mesoporous molecular sieve raw powder is mixed with anhydrous ethanol and concentrated hydrochloric acid, and then filtered, washed, dried and the template agent is removed to obtain a high specific surface area mesoporous molecular sieve.

5. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to claim 4, in, The auxiliary template agent is selected from one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetraisopropylammonium hydroxide.

6. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to claim 4, in, The template has the general formula shown in formula (a); [NR 1 R 2 R 3 R 4 + X - ; Formula (a);​ Among them, R 1 Represents C 12 -C 30 A straight chain or branched alkyl group; R 2 , R 3 and R 4 Same or different, each is C 1 -C 4 A straight chain or branched alkyl group; X represents a halogen element, preferably one or more selected from fluorine, chlorine and bromine; Preferably, the template is selected from one or more of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride and octadecyltrimethylammonium chloride.

7. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to claim 4, in, The low-carbon alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol; And / or, the silicon source is an organic silicon-containing compound and / or an inorganic silicon-containing compound; And / or, the weight ratio of the template, the auxiliary template, the low-carbon alcohol, the silicon source and the deionized water is 1: (0.1-1.2): (0.1-4.0): (0.5-6.0): (1-20); And / or, the contacting conditions include: temperature of 10-70°C and time of 0.5-10h; And / or, the crystallization conditions include: temperature of 10-120° C. and time of 2-48 h.

8. The sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to any one of claims 1 to 7, in, The specific surface area of ​​the sulfonated modified high specific surface area mesoporous molecular sieve catalyst is 500-1200m 2 / g, pore volume 0.7-1.4cm 3 / g, and the average pore size is 1.5-2.6nm.

9. A method for preparing a sulfonated modified high specific surface area mesoporous molecular sieve catalyst, It is characterized in that The preparation method comprises: contacting a high specific surface area mesoporous molecular sieve with a halosulfonic acid for sulfonation treatment to obtain a sulfonated modified high specific surface area mesoporous molecular sieve catalyst; Wherein, the weight ratio of the high specific surface area mesoporous molecular sieve to the halosulfonic acid is 1:(0.2-1.5).

10. The preparation method according to claim 9, in, The weight ratio of the high specific surface area mesoporous molecular sieve to the halosulfonic acid is 1:(0.4-0.8); And / or, the specific surface area of ​​the high specific surface area mesoporous molecular sieve is 800-1600m 2 / g, average pore diameter is 2-5nm, pore volume is 0.7-1.8mL / g; Preferably, the high specific surface area mesoporous molecular sieve has a specific surface area of ​​900-1400 m 2 / g, average pore diameter is 2-4nm, pore volume is 0.9-1.6mL / g; and / or, the halosulfonic acid is selected from one or more of fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid and iodosulfonic acid, preferably chlorosulfonic acid; And / or, the contacting conditions include: temperature of 30-80° C. and time of 0.2-8 hours.

11. A sulfonated modified high specific surface area mesoporous molecular sieve catalyst prepared by the preparation method according to claim 9 or 10.

12. Use of the sulfonated modified high specific surface area mesoporous molecular sieve catalyst according to any one of claims 1 to 8 and 11 in the synthesis reaction of cyclohexyl acetate.

13. The use according to claim 12, in, The application comprises: in the presence of water-carrying agent cyclohexane, contacting the sulfonated modified high specific surface area mesoporous molecular sieve catalyst, acetic acid and cyclohexanol to react; Preferably, the conditions for the contact reaction include: a reaction temperature of 70-130° C. and a reaction time of 0.5-8 h; And / or, the weight ratio of the acetic acid, the cyclohexanol, the sulfonated modified high specific surface area mesoporous molecular sieve catalyst and the water-carrying cyclohexane is 1:(1-10):(0.01-0.1):(0.5-6).

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