Supported solid acid catalyst for reaction for preparing isosorbide through sorbitol dehydration as well as preparation method and application of supported solid acid catalyst

Abstract

The invention discloses a supported solid acid catalyst for a reaction of preparing isosorbide through sorbitol dehydration and a preparation method and application thereof.The preparation method of the catalyst comprises the steps that sulfate is added into a surfactant solution with a certain concentration and stirred to be uniform, then a certain amount of molecular sieves are added, stirring is conducted for 3-8 h at the room temperature, then aging is conducted for 12-24 h, and the supported solid acid catalyst is obtained. And drying at 80-200 DEG C for 2-12 hours, and roasting at 400-900 DEG C for 2-8 hours to obtain the supported sulfated copper oxide solid acid catalyst. An adopted catalyst system is based on a molecular sieve loaded sulphated copper oxide solid acid catalyst, isosorbide is prepared through a reaction of a sorbitol aqueous solution in a fixed bed, and the technical process is high in sorbitol conversion rate and isosorbide yield. The product is easy to recover and high in purity, and the catalyst used in the method has higher selectivity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalytic chemistry, and particularly relates to a supported solid acid catalyst for sorbitol dehydration to prepare isosorbide, and a preparation method and application thereof. BACKGROUND

[0002] Isosorbide is a new type of biomass-based functional diol material, and is an important bio-based platform molecule, which has wide applications in food and cosmetic, pharmaceutical, plastic and polymer industries. In the traditional industry, a batch reactor is mainly used to prepare isosorbide by using concentrated sulfuric acid as a catalyst through a vacuum melting method. However, there are some disadvantages, such as corrosion of equipment, pollution of environment, difficulty in subsequent purification, and the like. In addition, the product quality is not easy to guarantee, and the obtained crude product often has a very deep color, which needs to be refined for many times to meet the requirements of its use. Therefore, it is of great significance to develop a new method for preparing isosorbide from sorbitol, and to realize continuous, stable and high-quality production of the product. Compared with the batch process, the fixed bed catalytic reaction significantly improves the production efficiency of isosorbide. However, there are few studies on the solid catalyst for the reaction of continuous dehydration of sorbitol to prepare isosorbide in a fixed bed. For example, Chinese patent CN101492457A discloses that a tetravalent metal oxide modified by H3PO4 is used as a catalyst to prepare isosorbide through a dehydration reaction at a reaction temperature of 250-300℃, and the selectivity of isosorbide is 63.49% and the yield is 62.23%; Chinese patent CN101691376A discloses that a solid-supported heteropoly acid is used as a catalyst, and the selectivity of isosorbide reaches 75.2% and the yield reaches 71.4%; in addition, literature (Catalysis Communications, Volume 12, Issue 6, 2011, 544-547) reports a study on the dehydration of sorbitol to prepare isosorbide using sulfated copper oxide as a catalyst, and the conversion rate of sorbitol is 99.7% and the selectivity of isosorbide is 67.5%, but the reaction is deactivated quickly. In addition, there are problems such as high reaction temperature, high energy consumption, low selectivity and yield of the product, and easy coking and agglomeration of the catalyst. SUMMARY

[0003] In view of the problems in the prior art, the present application discloses a supported solid acid catalyst for the dehydration of sorbitol to prepare isosorbide in a fixed bed reaction, and a preparation method and application thereof.

[0004] In order to achieve the above-mentioned purposes of the present application, the following technical solutions are adopted:

[0005] The application discloses a preparation method of a supported copper oxide sulfate solid acid catalyst, which comprises the following steps: adding copper sulfate pentahydrate into a surfactant aqueous solution with a certain concentration, uniformly stirring, adding molecular sieves, stirring at room temperature for 2-8 hours, aging for 8-12 hours, removing the solvent by drying, and then calcining under air at 400-900 DEG C for 2-10 hours to obtain the supported copper oxide sulfate solid acid catalyst with high dispersion.

[0006] Further, the molecular sieve is one of H-beta, HZSM-5, H-MOR, MCM-41 and SBA-15.

[0007] Further, the mass ratio of the copper sulfate pentahydrate to the molecular sieve is 0.05-0.3:1.

[0008] Further, an auxiliary metal sulfate is added into the surfactant aqueous solution, the auxiliary metal is at least one of Zr, Ni and Al, the molar ratio of the auxiliary metal sulfate to copper sulfate is 0.05-0.2:1, preferably 0.1-0.12:1.

[0009] Further, the surfactant is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and Tween 80, and the concentration of the surfactant aqueous solution is 1*10 -4 ~1 mol / L. -1 , preferably 1*10 -4 ~0.1 mol / L. -1 .

[0010] Further, the drying temperature is 80-200 DEG C, the drying time is 2-12 hours, the calcining temperature is 400-800 DEG C, and the calcining time is 2-10 hours.

[0011] The application further discloses an application of the supported copper oxide sulfate solid acid catalyst in a reaction of catalyzing sorbitol dehydration to prepare isosorbide, the catalyst is filled in a fixed bed reactor, the catalytic bed is heated to 150-300 DEG C, preferably 180-250 DEG C under N2 protection, the obtained mixed gas raw material is obtained after the sorbitol aqueous solution is vaporized by heating, and the mixed gas raw material is fed into the catalyst bed of the fixed bed reactor to react.

[0012] Further, the concentration of the sorbitol aqueous solution is 5-30 wt%, preferably 10-15 wt%; and the liquid hourly space velocity of the sorbitol aqueous solution is 0.5-8 h -1 , preferably 1-4 h -1 .

[0013] Compared with the prior art route, the method has the following characteristics:

[0014] 1) The supported sulfated copper oxide solid acid catalyst prepared by the traditional method has problems of low specific surface area, easy caking and carbon deposition. Therefore, the patent introduces molecular sieve as a carrier to modify the sulfated copper oxide catalyst, and adds a certain amount of surfactant during preparation, aiming to increase the specific surface area of the catalyst while improving the dispersion of the active component sulfated copper oxide on the carrier, and prepare a supported sulfated copper oxide catalyst with high dispersion of active components. In addition, some other metal sulfate additives are introduced to improve the anti-carbon and sintering capacity through synergistic effect with active metal copper. In addition, the molecular sieve can promote the rapid diffusion of reactants and products due to its special pore structure, reduce diffusion limitation, and improve its reaction rate and selectivity.

[0015] 2) The method for preparing isosorbide by using the supported sulfated copper oxide solid acid catalyst prepared by the present application has a sorbitol conversion rate of 100% and an isosorbide yield of more than 80%. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 XRD pattern of the catalyst sample in Example 1.

[0017] Figure 2 Nitrogen adsorption-desorption isotherm of the catalyst sample in Example 1.

[0018] Figure 3 HPLC pattern of the reaction solution after catalytic reaction of the sorbitol aqueous solution in Example 1. DETAILED DESCRIPTION

[0019] The method described in the present application will be described in detail below in combination with specific examples.

[0020] In the embodiments of the present application, the molecular sieves Hβ, HZSM-5, H-MOR, MCM-41 and SBA-15 are all purchased from Dalian Zel Catalytic Material Co., Ltd.

[0021] In the embodiments of the present application, the sample obtained after catalytic reaction of the sorbitol aqueous solution is analyzed by high performance liquid chromatography, high performance liquid chromatography (LC-10ADvp), chromatographic column (kromasil-NH2), mobile phase (volume ratio of acetonitrile: water = 2:1, 0.6 mL·min -1 ), column temperature 35℃, differential refractive index detector (Shimadzu RID-10A).

[0022] Example 1

[0023] 10 mL of sorbitol aqueous solution with a concentration of 1×10 -3 mol·L -10.873 g of CuSO4·5H2O was added to the aqueous solution of sodium dodecyl sulfate surfactant, stirred evenly, and then 3.2 g of Hβ molecular sieve was added. The mixture was stirred at room temperature for 4 h, aged for 10 h, dried at 110 ° C for 12 h, and finally calcined at 600 ° C in air for 4 h to obtain 15% CuO-SO x / Hβ-600 solid acid catalyst. The catalyst was characterized by XRD, and its spectrum is as follows Figure 1 As shown in the figure, it can be seen that the parent copper sulfate is formed after calcination at 600℃. In addition to copper sulfate, a new phase Cu2OSO4 also appears in the sample. The Hβ crystal form is not destroyed after high-temperature calcination. The sulfated copper oxide active component is successfully loaded on the carrier Hβ. The catalyst was characterized by nitrogen adsorption-desorption, and its spectrum is shown in the figure below. Figure 2 The sample shows the characteristics of type IV isotherm and has a large specific surface area of ​​389m 2 ·g -1 .

[0024] Example 1 The catalyst was used in the catalytic conversion reaction of sorbitol aqueous solution. The process was as follows: the catalyst powder was crushed into tablets, sieved through a 20-40 mesh screen, and 0.6 g of the catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked and sealed, the catalyst bed was programmed to 200° C. under N2 flow protection and preheated for 40 minutes. Then, a 10 wt% sorbitol aqueous solution (liquid hourly space velocity 2h -1 ) was pumped into the system, vaporized and reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results showed that the sorbitol conversion rate was 100% and the isosorbide yield was 71.0%. The samples collected after the reaction were analyzed by high performance liquid chromatography. Figure 3 shown.

[0025] Example 2

[0026] Take 10mL of the solution with a concentration of 1×10 -3 mol·L -1 0.556 g of CuSO4·5H2O was added to the aqueous solution of sodium dodecyl sulfate surfactant, stirred evenly, and then 3.2 g of Hβ molecular sieve was added. The mixture was stirred at room temperature for 3 h, aged for 12 h, dried at 80 ° C for 10 h, and finally calcined at 400 ° C in air for 10 h to obtain 10% CuO-SO x / Hβ-400 solid acid catalyst.

[0027] Example 2 The catalyst was used for the catalytic conversion reaction of sorbitol aqueous solution. The experimental steps were repeated in Example 1, with the only difference being that the catalyst bed temperature was raised to 220°C and the liquid hourly space velocity of the catalytic reaction was 1.5h -1", the rest of the conditions unchanged, the reaction results are: the collected liquid sample after 6h reaction was analyzed, the results showed that the conversion rate of sorbitol was 98.6%, and the yield of isosorbide was 62.4%.

[0028] Example 3

[0029] Take 10mL of 1×10 -3 mol·L -1 of sodium dodecyl sulfate surfactant aqueous solution, add 0.556g CuSO4·5H2O, stir uniformly, then add 3.2g of HZSM-5 molecular sieve, stir at room temperature for 3h, then age for 12h, dry at 80℃ for 10h, then calcine at 800℃ under air for 3h to obtain 10% CuO-SO x / HZSM-5-800 solid acid catalyst.

[0030] The catalyst of Example 3 was applied to the catalytic conversion reaction of sorbitol aqueous solution, and the experimental steps were repeated in Example 2. The reaction results are: the collected liquid sample after 6h reaction was analyzed, the results showed that the conversion rate of sorbitol was 99.8%, and the yield of isosorbide was 58.6%.

[0031] Example 4

[0032] Take 10mL of 1×10 -3 mol·L -1 of sodium dodecyl sulfate surfactant aqueous solution, add 0.263g CuSO4·5H2O, stir uniformly, then add 3.2g of MCM-41 molecular sieve, stir at room temperature for 3h, then age for 12h, dry at 80℃ for 10h, then calcine at 700℃ under air for 2h to obtain 5% CuO-SO x / MCM-41-700 solid acid catalyst.

[0033] The catalyst of Example 4 was applied to the catalytic conversion reaction of sorbitol aqueous solution, and the experimental steps were repeated in Example 2. The reaction results are: the collected liquid sample after 6h reaction was analyzed, the results showed that the conversion rate of sorbitol was 100%, and the yield of isosorbide was 60.5%.

[0034] Example 5

[0035] Take 10mL of 1×10 -1 mol·L x of sodium dodecyl sulfate surfactant aqueous solution, add 1.251g CuSO4·5H2O, stir uniformly, then add 3.2g of Hβ molecular sieve, stir at room temperature for 3h, then age for 12h, dry at 100℃ for 11h, then calcine at 550℃ under air for 6h to obtain 20% CuO-SO x / Hβ-550 solid acid catalyst.

[0036] The catalyst of Example 5 was used in the catalytic conversion reaction of sorbitol aqueous solution. The experimental steps were as follows: the catalyst powder was crushed into tablets, sieved through a 20-40 mesh screen, and 0.6 g of the catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked and sealed, the catalyst bed was programmed to 180°C under N2 flow protection and preheated for 40 minutes. Then, a 15 wt% sorbitol aqueous solution (liquid hourly space velocity 1 h -1 ) was pumped into the system, vaporized and reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results showed that the sorbitol conversion rate was 100% and the isosorbide yield was 64.5%.

[0037] Example 6

[0038] Take 10mL of the solution with a concentration of 1×10 -2 mol·L -1 0.873g CuSO4·5H2O and 0.124g Zr(SO4)2·4H2O were added to the aqueous solution of sodium dodecylbenzenesulfonate surfactant and stirred evenly. Then 3.2g Hβ molecular sieve was added and stirred at room temperature for 5h. After that, it was aged for 8h, dried at 110℃ for 12h, and finally calcined at 750℃ in air for 3h to obtain 15% Zr-CuO-SO x / Hβ-750 solid acid catalyst.

[0039] The catalyst of Example 6 was applied to the catalytic conversion reaction of sorbitol aqueous solution. The experimental steps were as follows: the powder was pressed into tablets and crushed, and sieved through 20-40 mesh to obtain 15% Zr-CuO-SO x / Hβ-750 catalyst. 0.6g of 20-40 mesh catalyst was loaded into the constant temperature section of the tubular fixed bed reactor. After the system was checked and sealed, the catalyst bed was programmed to 230℃ under N2 flow protection and preheated for 40 minutes. Then, 15wt% sorbitol aqueous solution (liquid hourly space velocity 2.5h -1 ) was pumped into the system, vaporized and reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results showed that the sorbitol conversion rate was 99.7% and the isosorbide yield was 63.1%.

[0040] Example 7

[0041] Take 10mL of the solution with a concentration of 1×10 -4 mol·L -1CuSO4-5H2O, 0.233 g Al2(SO4)3-18H2O were stirred uniformly, 3.2 g of Hβ zeolite was added, stirred at room temperature for 5 h, then aged for 24 h, dried at 110 °C for 12 h, and calcined at 650 °C for 4 h under air to obtain a 15%Al-CuO-SO x / Hβ-650 solid acid catalyst.

[0042] The catalyst of Example 7 was applied to the catalytic conversion reaction of an aqueous sorbitol solution. The experimental procedure was as follows: the powder was pressed into a tablet and crushed, sieved to 20-40 mesh, and 0.6 g of the 15%Al-CuO-SO x / Hβ-650 catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked for sealing, the catalyst bed was preheated to 240 °C under N2flow for 40 min, and then 10 wt% aqueous sorbitol solution (liquid hourly space velocity 2 h -1 ) was pumped into the system, vaporized, and reacted through the catalyst bed. The reaction mixture was cooled in an ice water bath, and the liquid collected after 6 h of reaction was sampled for analysis. The results were as follows: sorbitol conversion 100%, and isosorbide yield 80.1%.

[0043] Example 8

[0044] An aqueous solution of 10 mL of cetyltrimethylammonium bromide surfactant with a concentration of 0.1 mol·L -1 was prepared. 0.873 g CuSO4-5H2O and 0.233 g Al2(SO4)3-18H2O were stirred uniformly, 3.2 g of H-MOR zeolite was added, stirred at room temperature for 3 h, then aged for 12 h, dried at 110 °C for 12 h, and calcined at 600 °C for 4 h under air to obtain a 15%Al-CuO-SO x / H-MOR-600 solid acid catalyst.

[0045] The catalyst of Example 8 was applied to the catalytic conversion reaction of an aqueous sorbitol solution. The experimental procedure was as follows: the powder was pressed into a tablet and crushed, sieved to 20-40 mesh, and 0.6 g of the 15%Al-CuO-SO x / H-MOR-600 catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked for sealing, the catalyst bed was preheated to 220 °C under N2flow for 40 min, and then 5 wt% aqueous sorbitol solution (liquid hourly space velocity 3 h -1 ) was pumped into the system, vaporized, and reacted through the catalyst bed. The reaction mixture was cooled in an ice water bath, and the liquid collected after 6 h of reaction was sampled for analysis. The results were as follows: sorbitol conversion 100%, and isosorbide yield 65.8%.

[0046] Example 9

[0047] Take 10 mL concentration of 1 x 10 -3 mol·L -1 -1 surfactant aqueous solution of tetradecyl trimethyl ammonium bromide, 0.873 g CuSO4·5H2O, 0.233 g Al2(SO4)3·18H2O, after stirring evenly, 3.2 g of HZSM-5, stirring at room temperature for 3 h, then aging 12 h, drying at 110 ℃ for 12 h, and then calcining at 650 ℃ under air for 4 h to obtain 15% Al-CuO-SO x / HZSM-5-650 solid acid catalyst.

[0048] The catalyst of Example 9 is applied to the catalytic conversion reaction of sorbitol aqueous solution, and the experimental steps are as follows: the powder is pressed into a tablet and crushed, 20-40 mesh is screened, and 15% Al-CuO-SO x / HZSM-5-650 catalyst is obtained. 0.6 g of 20-40 mesh catalyst is loaded into the constant temperature section of the tubular fixed bed reactor. After the system is checked for sealing, the catalyst bed is programmed to heat to 200 ℃ under the protection of N2 flow for 40 min, and then 20 wt% sorbitol aqueous solution (liquid hourly space velocity 1.5 h -1 ) is pumped into the system, vaporized and reacted through the catalyst bed, and the reaction mixture is cooled in an ice water bath. The liquid collected after 6 h of reaction is sampled for analysis, and the results show that the conversion rate of sorbitol is 100% and the yield of isosorbide is 70.2%.

[0049] Example 10

[0050] Take 10 mL concentration of 0.5 mol·L -1 -1 surfactant aqueous solution of Tween 80, 0.873 g CuSO4·5H2O, 0.092 g NiSO4·6H2O (0.35 mmol), after stirring evenly, 3.2 g of MCM-41 molecular sieve, stirring at 80 ℃ for 8 h, then aging 24 h, drying at 110 ℃ for 8 h, and then calcining at 650 ℃ under air for 8 h to obtain 15% Ni-CuO-SO x / MCM-41-650 solid acid catalyst.

[0051] The catalyst of Example 10 is applied to the catalytic conversion reaction of sorbitol aqueous solution, and the experimental steps are as follows: the powder is pressed into a tablet and crushed, 20-40 mesh is screened, and 15% Ni-CuO-SO x / MCM-41-650 catalyst. 0.6 g of 20-40 mesh catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked for seal, the catalyst bed was programmed to heat to 220 °C under the protection of N2flow for 40 min, then 5 wt% sorbitol aqueous solution (liquid hourly space velocity 3.5 h -1 ) was pumped into the system, vaporized and reacted through the catalyst bed, the reaction mixture was cooled by ice water bath, the liquid collected in 6 h was analyzed by high performance liquid chromatography, the results were 100% conversion of sorbitol and 75.2% yield of isosorbide.

[0052] Example 11

[0053] 10 mL of 1 x 10 -3 mol·L -1 aqueous solution of sodium dodecyl sulfate surfactant was added with 1.251 g CuSO4·5H2O and 0.084 g Ti(SO4)2, stirred uniformly, then 3.2 g of SBA-15 molecular sieve was added, stirred for 3 h at room temperature, then aged for 12 h, dried at 110 °C for 12 h, and calcined at 650 °C for 4 h under air to obtain Ti-20% CuO-SO x / Hβ-650 solid acid catalyst.

[0054] The catalyst of Example 11 was applied to the catalytic conversion reaction of sorbitol aqueous solution, the experimental steps were as follows: the powder was pressed into a tablet and crushed, sieved to 20-40 mesh to obtain 20% Ti-CuO-SO x / SBA-15-650 catalyst. 0.6 g of 20-40 mesh catalyst was loaded into the constant temperature section of a tubular fixed bed reactor. After the system was checked for seal, the catalyst bed was programmed to heat to 220 °C under the protection of N2flow for 40 min, then 10 wt% sorbitol aqueous solution (liquid hourly space velocity 2.5 h -1 ) was pumped into the system, vaporized and reacted through the catalyst bed, the reaction mixture was cooled by ice water bath, the liquid collected in 6 h was sampled and analyzed, the results were 99.6% conversion of sorbitol and 76.4% yield of isosorbide.

[0055] Comparative Example 1

[0056] 10 mL of deionized water was added with 3 g CuSO4·5H2O, stirred for 5 h at room temperature, aged for 21 h, dried at 110 °C for 12 h, and calcined at 650 °C for 4 h under air to obtain CuO-SO x -650 solid acid catalyst.

[0057] The powder was pressed into a tablet and crushed, sieved to 20-40 mesh to obtain CuO-SO x-650 catalyst. 0.6g of 20-40 mesh catalyst was loaded into the constant temperature section of the tubular fixed bed reactor. After the system was checked and sealed, the catalyst bed was programmed to 240℃ under N2 flow protection and preheated for 40min. Then, 10wt% sorbitol aqueous solution (liquid hourly space velocity 2h -1 ) was pumped into the system, and after vaporization, it was reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results are shown in Table 1.

[0058] Comparative Example 2

[0059] Take 3.2g of Hβ molecular sieve, crush the powder into tablets, sieve through 20-40 mesh, and load 0.6g of the 20-40 mesh catalyst into the constant temperature section of the tubular fixed bed reactor. After checking the system seal, the catalyst bed is programmed to 240℃ under N2 flow protection and preheated for 40 minutes. Then, 10wt% sorbitol aqueous solution (liquid hourly space velocity 2h -1 ) was pumped into the system, and after vaporization, it was reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results are shown in Table 1.

[0060] Comparative Example 3

[0061] Take 10mL of the solution with a concentration of 1×10 -4 mol·L -1 0.873g CuSO4·5H2O and 0.233g Al2(SO4)3·18H2O were added to the aqueous solution of sodium dodecylbenzenesulfonate surfactant and stirred evenly. Then 3.2g γ-Al2O3 was added and stirred at room temperature for 5h. The mixture was aged for 24h, dried at 110℃ for 12h, and calcined at 650℃ in air for 4h to obtain 15% Al-CuO-SO x / γ-Al2O3-650 solid acid catalyst.

[0062] The catalyst powder of Comparative Example 3 was crushed and sieved through a 20-40 mesh sieve. 0.6 g of the 20-40 mesh catalyst was loaded into the constant temperature section of the tubular fixed bed reactor. After the system was checked and sealed, the catalyst bed was programmed to 200°C under N2 flow protection and preheated for 40 minutes. Then, a 10 wt% sorbitol aqueous solution (liquid hourly space velocity 2h -1 ) was pumped into the system, and after vaporization, it was reacted through the catalyst bed. The reaction mixture was cooled in an ice-water bath. The liquid collected after 6 hours of reaction was sampled and analyzed. The results are shown in Table 1.

[0063] Table 1

[0064] Example Sorbitol conversion (%) Isosorbide selectivity (%) Isosorbide yield (%) Comparative Example 1 99.8 52.0 51.9 Comparative Example 2 99.0 44.6 44.2 Comparative Example 3 99.6 59.9 59.7 Example 7 100.0 80.1 80.1 .

Claims

1. A method for preparing a supported sulfated copper oxide solid acid catalyst, characterized in that Copper sulfate pentahydrate is added to a surfactant aqueous solution of a certain concentration, stirred evenly, and then molecular sieves are added. The mixture is stirred at room temperature for 2-8 hours, aged for 8-12 hours, dried to remove the solvent, and then calcined at 400-900°C in air for 2-10 hours to obtain a highly dispersed supported sulfated copper oxide solid acid catalyst.

2. The method for preparing a supported sulfated copper oxide solid acid catalyst as claimed in claim 1, wherein The molecular sieve is one of Hβ, HZSM-5, H-MOR, MCM-41, and SBA-15.

3. The method for preparing a supported sulfated copper oxide solid acid catalyst as claimed in claim 1, wherein The mass ratio of copper sulfate pentahydrate to molecular sieve is 0.05-0.3:

1.

4. The method for preparing a supported sulfated copper oxide solid acid catalyst as claimed in claim 1, wherein Auxiliary metal sulfate is also added to the surfactant aqueous solution, wherein the auxiliary metal is at least one of Zr, Ni and Al, and the molar ratio of the auxiliary metal sulfate to copper sulfate is 0.05-0.2:1, preferably 0.1-0.12:

1.

5. The method for preparing a supported sulfated copper oxide solid acid catalyst as claimed in claim 1, wherein The surfactant is one of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, and Tween 80. The concentration of the surfactant aqueous solution is 1×10 -4 ~1 mol·L -1 , preferably 1×10 -4 ~0.1 mol·L -1 .

6. The method for preparing a supported sulfated copper oxide solid acid catalyst as claimed in claim 1, wherein The drying temperature is 80-200° C., the drying time is 2-12 hours, the calcination temperature is 400-800° C., and the calcination time is 2-10 hours.

7. A supported sulfated copper oxide solid acid catalyst prepared by the method according to any one of claims 1 to 6.

8. Use of a supported sulfated copper oxide solid acid catalyst as claimed in claim 7 in catalyzing the dehydration of sorbitol to produce isosorbide.

9. The use according to claim 8, characterized in that The catalyst is filled in a fixed bed reactor, and the catalyst bed is heated to 150-300 °C, preferably 180-250 °C, under N2 protection. After the sorbitol aqueous solution is heated and vaporized, the resulting mixed gas feed is passed into the catalyst bed of the fixed bed reactor for reaction.

10. The use according to claim 8, characterized in that The concentration of sorbitol aqueous solution is 5-30wt%, preferably 10-15wt%; the liquid hourly space velocity of sorbitol aqueous solution feed is 0.5-8 h -1 , preferably 1 to 4 hours -1 .

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