A method for preparing carbonyl sulfide hollow nanosphere hydrolysis catalyst

Abstract

The present invention discloses a preparation method of a carbonyl sulfide nano-hollow sphere hydrolysis catalyst. The method comprises the following steps: First, glucose carbon spheres are prepared by a hydrothermal reaction. Then, aluminum ions are loaded onto the glucose carbon spheres by an aluminum chloride solution. After drying and calcination, Al2O3 hollow spheres are obtained. Finally, the Al2O3 hollow spheres are impregnated in a zirconium nitrate solution. After drying and calcination, Zr@γ-Al2O3 hollow spheres are obtained, which are the carbonyl sulfide nano-hollow sphere hydrolysis catalyst. The hydrolysis catalyst prepared by the preparation method provided by the present invention has high catalytic hydrolysis activity in a low-temperature environment. When the reaction temperature is 80 °C, the catalytic efficiency of the prepared nano-hollow sphere hydrolysis catalyst can reach up to 95%, and its industrial cost is low and the carbonyl sulfide removal rate is high.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrolysis catalysts, and in particular relates to a method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst. Background Art

[0002] Carbonyl sulfide in blast furnace gas is one of the main pollutants causing sulfur pollution in the atmosphere. Excessive emission of carbonyl sulfide will cause serious harm to human body, buildings, plants and soil. Catalytic hydrolysis under low temperature environment is the most potential and application prospect of carbonyl sulfide purification technology for blast furnace gas. The hydrolysis catalyst used in the hydrolysis catalytic process is the key to whether carbonyl sulfide can meet the emission standards. The performance of the hydrolysis catalyst determines the desulfurization accuracy.

[0003] At present, the hydrolysis catalysts used for the removal of carbonyl sulfide in blast furnace gas mainly include hydrotalcite-like compound catalysts, transition metal oxide catalysts and metal oxide catalysts. Hydrotalcite-like catalysts have a good effect on the removal of carbonyl sulfide in the hydrolysis catalytic process, but in the air atmosphere, the hydrolysis catalyst is easily poisoned by sulfate, resulting in a decrease in the catalytic activity of the hydrolysis catalyst; the transition metal oxide catalyst has good antioxidant properties, but the industrial cost of the catalyst is high and the service life is short, and the reaction activity is low and the catalytic effect is not high under low temperature conditions, which limits its application in industrial production; the metal oxide catalyst mainly includes Al2O3, TiO2, and composite metal iron-manganese oxides. Although these catalysts have a certain hydrolysis catalytic effect, the industrial cost is still relatively high. At the same time, due to the limitations of sulfur capacity and desulfurization accuracy, they cannot meet the emission standards for industrial fine desulfurization. Summary of the invention

[0004] The object of the present invention is to overcome the deficiencies in the above-mentioned prior art and provide a method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst. The hydrolysis catalyst prepared by the method has high catalytic hydrolysis activity under low temperature environment. When the reaction temperature is 80°C, the catalytic efficiency of the prepared nano hollow sphere hydrolysis catalyst can reach up to 95%, and the industrial cost is low and the carbonyl sulfide removal rate is high.

[0005] To achieve the above object, the technical solution adopted by the present invention is to provide a method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst, comprising the following steps:

[0006] Step 1, preparing glucose carbon balls: dissolving glucose in distilled water and stirring thoroughly to obtain a glucose solution, taking the completely dissolved glucose solution for hydrothermal reaction, and after the hydrothermal reaction, allowing the solution to cool naturally to room temperature, washing and filtering the solution until the solution becomes clear, drying the precipitate obtained by filtration and grinding it into powder to obtain carbon balls;

[0007] Step 2, preparing Al2O3 hollow spheres: adding aluminum chloride to a water-alcohol mixed solution and stirring rapidly to completely dissolve the aluminum chloride to obtain an aluminum chloride solution, adding the carbon balls prepared in the step 1 to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, ultrasonically oscillating the carbon ball mixed solution for 0.5h-1h to load aluminum ions on the carbon balls, then adding urea to the oscillated carbon ball mixed solution, and stirring uniformly in a water bath at 60°C-70°C for 12h-18h, then filtering to obtain a brown solid, washing and drying the brown solid, and then sending it to a muffle furnace for calcination to obtain Al2O3 hollow spheres;

[0008] Step 3: Prepare Zr@γ-Al2O3 hollow spheres: immerse the Al2O3 hollow spheres obtained in step 2 in a zirconium nitrate solution for 9h-12h, then take out, dry and calcine to obtain finished Zr@γ-Al2O3 hollow spheres, i.e., carbonyl sulfide nano hollow sphere hydrolysis catalysts.

[0009] Furthermore, the hydrothermal reaction in step 1 is to place the glucose solution in a polytetrafluoroethylene hydrothermal reactor, and then place the reactor in an electric heated blast drying oven to react at a constant temperature of 150° C.-250° C. for 2 h-10 h.

[0010] Furthermore, the drying conditions in step 1 to step 3 are all to dry in a blast drying oven at a constant temperature of 60° C.-80° C. for 6 h-12 h.

[0011] Furthermore, the washing in step 1 to step 3 is specifically washing with deionized water and anhydrous ethanol alternately.

[0012] Furthermore, the calcination temperature for preparing Al2O3 hollow spheres in step 2 is 650°C-1150°C, and the calcination time is 1h-4h.

[0013] Furthermore, in the step 3, the calcination temperature for preparing Zr@γ-Al2O3 hollow spheres is 400°C-700°C, and the calcination time is 2h-3h.

[0014] Furthermore, the mass concentration of the zirconium nitrate solution in step three is 4%-10%.

[0015] Furthermore, the amount of glucose used in step 1 is 6 g, the amount of distilled water used is 100 mL, and the amount of glucose solution used for the hydrothermal reaction is 70 mL.

[0016] Furthermore, in the step 2, the amount of aluminum chloride used is 20 mmol-50 mmol, the amount of carbon balls used is 1 g, and the amount of urea used is 0.1 mol.

[0017] Furthermore, in the step 2, the amount of the water-alcohol mixed solution is 120 mL, the water-alcohol mixed solution is composed of anhydrous ethanol and water, and the mass of the anhydrous ethanol accounts for 1%-99% of the mass of the water-alcohol mixed solution.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] 1. The nano hollow sphere hydrolysis catalyst prepared by the present invention has good removal activity under low temperature environment. When the reaction temperature is 80°C, the catalytic efficiency of the prepared nano hollow sphere hydrolysis catalyst can reach up to 95%-98%. Compared with the transition metal, precious metal and rare earth metal hydrolysis catalysts currently used in industry, its industrial cost is lower and the carbonyl sulfide removal rate is higher.

[0020] 2. The nano hollow sphere hydrolysis catalyst prepared by the present invention has a high catalytic hydrolysis activity in the low temperature range, which greatly reduces the requirements for equipment. Compared with the iron-manganese type hydrolysis catalyst, the deactivated nano hollow sphere hydrolysis catalyst can also be used in multiple fields, such as being used as a precipitant in the papermaking industry or as a flocculant in water treatment. This not only reduces the subsequent solid waste treatment, but also complies with the "dual carbon" concept currently advocated by the country.

[0021] 3. The nano hollow sphere hydrolysis catalyst prepared by the present invention reduces the pollution to the atmospheric environment to a certain extent. Experiments have proved that the nano hollow sphere hydrolysis catalyst prepared by the present invention converts organic sulfur - carbonyl sulfide into inorganic sulfur - hydrogen sulfide, and the hydrolysis product hydrogen sulfide can be used as raw gas for subsequent industrial production.

[0022] The present invention is further described in detail below through the accompanying drawings and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the SEM image of the carbon sphere prepared in Example 1 of the present invention.

[0024] Figure 2 It is the removal rate of carbonyl sulfide catalytic hydrolysis by the Zr@γ-Al2O3 hollow sphere hydrolysis catalyst prepared in Examples 1-4 of the present invention.

[0025] Figure 3 It is the removal rate of carbonyl sulfide hydrolysis catalyzed by the nano hollow sphere hydrolysis catalyst prepared in Examples 5-7 of the present invention. DETAILED DESCRIPTION

[0026] Embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although certain embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be construed as being limited to the embodiments described herein, which are instead provided for a more thorough and complete understanding of the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not intended to limit the scope of protection of the present invention.

[0027] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0028] Embodiment 1

[0029] A method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst comprises the following steps:

[0030] Step 1, preparation of glucose carbon ball: 6g glucose was dissolved in 100mL distilled water and stirred thoroughly, 70mL of the completely dissolved glucose solution was placed in a 100mL polytetrafluoroethylene hydrothermal reactor, the reactor was placed in an electric blast drying oven, and the reaction was carried out at a constant temperature of 220°C for 4h. After the reaction, the reactor was naturally cooled to room temperature, the brown suspension liquid was taken out, and deionized water and anhydrous ethanol were used to wash and filter alternately until the filtered solution was a clear solution. The brown precipitate on the filter paper was placed in an electric blast drying oven and dried at a constant temperature of 80°C for 6 hours. After drying, it was ground into powder to obtain carbon balls, and its SEM picture was as shown below. Figure 1 As shown, it can be found that the surface of the obtained carbon balls is smooth and evenly distributed;

[0031] Step 2, preparing Al2O3 hollow spheres: adding 40mmol of aluminum chloride to 120mL of a water-alcohol mixed solution (containing 1% by mass of anhydrous ethanol) and stirring rapidly to dissolve it completely to obtain an aluminum chloride solution, taking 1g of the carbon ball prepared in the step 1 and adding it to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, placing the carbon ball mixed solution in a numerically controlled ultrasonic cleaner for ultrasonic oscillation for 1h to uniformly load the aluminum ions on the carbon balls, then taking 0.1mol of urea and adding it to the dispersed carbon ball mixed solution, stirring uniformly in a 70°C water bath for 12h, and filtering with a vacuum filtration pump to obtain a brown solid, washing the brown solid with deionized water and anhydrous ethanol alternately, and then drying it in a blast drying oven, drying it at a constant temperature of 60°C for 12 hours, and calcining the dried brown solid in a muffle furnace at 650°C for 2h to obtain Al2O3 hollow spheres;

[0032] Step 3, preparation of Zr@γ-Al2O3 hollow spheres: the Al2O3 hollow spheres obtained in the step 2 are fully immersed in a zirconium nitrate solution with a mass concentration of 4% for 9 hours, the Zr-loaded Al2O3 hollow spheres are taken out and dried at a constant temperature of 70°C for 10 hours, and calcined at 500°C for 2 hours to obtain finished Zr@γ-Al2O3 hollow spheres.

[0033] The method for catalytically removing carbonyl sulfide from blast furnace gas by hydrolysis using Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment comprises the following steps: 0.2 g of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst is loaded into a tubular furnace, the reaction temperature of the tubular furnace is 80°C, and then simulated blast furnace gas carbonyl sulfide gas is introduced into the tubular furnace filled with Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst, and gas components of the reacted gas are detected using a gas chromatograph; the gas flow rate of the simulated gas introduced into the tubular furnace is 50 mL / min, and the simulated blast furnace gas is composed of the following components at the following concentrations: COS is 213.0 mg / m 3 , the remainder is N2.

[0034] like Figure 2 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 86.42%.

[0035] Embodiment 2

[0036] A method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst comprises the following steps:

[0037] Step 1, preparation of glucose carbon ball: 6g glucose was dissolved in 100mL distilled water and stirred thoroughly, 70mL of the completely dissolved glucose solution was placed in a 100mL polytetrafluoroethylene hydrothermal reactor, the reactor was placed in an electric blast drying oven, and the reaction was carried out at a constant temperature of 150°C for 10h. After the reaction was completed, the reactor was naturally cooled to room temperature, the brown suspension liquid was taken out, and deionized water and anhydrous ethanol were used to wash and filter alternately until the filtered solution was a clear solution, the brown precipitate on the filter paper was placed in an electric blast drying oven, and dried at a constant temperature of 60°C for 12 hours. After drying, it was ground into powder to obtain carbon ball;

[0038] Step 2, preparation of Al2O3 hollow spheres: adding 20mmol of aluminum chloride to 120mL of a water-alcohol mixed solution (containing 25% by mass of anhydrous ethanol) and stirring rapidly to dissolve it completely to obtain an aluminum chloride solution, taking 1g of the carbon ball prepared in the step 1 and adding it to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, placing the carbon ball mixed solution in a numerically controlled ultrasonic cleaner for ultrasonic oscillation for 0.5h to uniformly load the aluminum ions on the carbon balls, then taking 0.1mol of urea and adding it to the dispersed carbon ball mixed solution, stirring uniformly in a 60°C water bath for 18h, filtering with a vacuum filtration pump to obtain a brown solid, washing the brown solid alternately with deionized water and anhydrous ethanol, and then drying it in a blast drying oven, drying it at a constant temperature of 70°C for 10 hours, and placing the dried brown solid in a muffle furnace at a temperature of 1150°C for 1h to obtain Al2O3 hollow spheres;

[0039] Step 3, preparation of Zr@γ-Al2O3 hollow spheres: the Al2O3 hollow spheres obtained in the step 2 are fully immersed in a zirconium nitrate solution with a mass concentration of 4% for 12 hours, the Zr-loaded Al2O3 hollow spheres are taken out and dried at a constant temperature of 80°C for 6 hours, and calcined at 400°C for 3 hours to obtain finished Zr@γ-Al2O3 hollow spheres.

[0040] The method for catalytically removing carbonyl sulfide from blast furnace gas by hydrolysis using Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment comprises the following steps: 0.2 g of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst is loaded into a tubular furnace, the reaction temperature of the tubular furnace is 80°C, and then simulated blast furnace gas carbonyl sulfide gas is introduced into the tubular furnace filled with Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst, and gas components of the reacted gas are detected using a gas chromatograph; the gas flow rate of the simulated gas introduced into the tubular furnace is 50 mL / min, and the simulated blast furnace gas is composed of the following components at the following concentrations: COS is 213.0 mg / m 3 , the remainder is N2.

[0041] like Figure 2 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 82.29%.

[0042] Embodiment 3

[0043] A method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst comprises the following steps:

[0044] Step 1, preparation of glucose carbon ball: 6g glucose was dissolved in 100mL distilled water and stirred thoroughly, 70mL of the completely dissolved glucose solution was placed in a 100mL polytetrafluoroethylene hydrothermal reactor, the reactor was placed in an electric blast drying oven, and the reaction was carried out at a constant temperature of 250°C for 2h. After the reaction was completed, the reactor was naturally cooled to room temperature, the brown suspension liquid was taken out, and deionized water and anhydrous ethanol were used to wash and filter alternately until the filtered solution was a clear solution. The brown precipitate on the filter paper was placed in an electric blast drying oven and dried at a constant temperature of 70°C for 10 hours. After drying, it was ground into powder to obtain carbon ball;

[0045] Step 2, preparation of Al2O3 hollow spheres: adding 50mmol of aluminum chloride to 120mL of a water-alcohol mixed solution (containing 75% by mass of anhydrous ethanol) and stirring rapidly to dissolve it completely to obtain an aluminum chloride solution, taking 1g of the carbon ball prepared in the step 1 and adding it to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, placing the carbon ball mixed solution in a numerically controlled ultrasonic cleaner for ultrasonic oscillation for 0.8h to uniformly load the aluminum ions on the carbon balls, then taking 0.1mol of urea and adding it to the dispersed carbon ball mixed solution, stirring uniformly in a 65°C water bath for 15h, filtering with a vacuum filtration pump to obtain a brown solid, washing the brown solid alternately with deionized water and anhydrous ethanol, and then drying it in a blast drying oven, drying it at a constant temperature of 80°C for 6 hours, and calcining the dried brown solid in a muffle furnace at 950°C for 4h to obtain Al2O3 hollow spheres;

[0046] Step 3, preparation of Zr@γ-Al2O3 hollow spheres: the Al2O3 hollow spheres obtained in the step 2 are fully immersed in a zirconium nitrate solution with a mass concentration of 4% for 10 hours, the Zr-loaded Al2O3 hollow spheres are taken out and dried at a constant temperature of 60°C for 12 hours, and calcined at 600°C for 2.5 hours to obtain finished Zr@γ-Al2O3 hollow spheres.

[0047] The method for catalytically removing carbonyl sulfide from blast furnace gas by hydrolysis using Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment comprises the following steps: 0.2 g of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst is loaded into a tubular furnace, the reaction temperature of the tubular furnace is 80°C, and then simulated blast furnace gas carbonyl sulfide gas is introduced into the tubular furnace filled with Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst, and gas components of the reacted gas are detected using a gas chromatograph; the gas flow rate of the simulated gas introduced into the tubular furnace is 50 mL / min, and the simulated blast furnace gas is composed of the following components at the following concentrations: COS is 213.0 mg / m 3 , the remainder is N2.

[0048] like Figure 2 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 86.27%.

[0049] Embodiment 4

[0050] A method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst comprises the following steps:

[0051] Step 1, preparation of glucose carbon ball: 6g glucose was dissolved in 100mL distilled water and stirred thoroughly, 70mL of the completely dissolved glucose solution was placed in a 100mL polytetrafluoroethylene hydrothermal reactor, the reactor was placed in an electric blast drying oven, and the reaction was carried out at a constant temperature of 210°C for 6h. After the reaction was completed, the reactor was naturally cooled to room temperature, the brown suspension liquid was taken out, and deionized water and anhydrous ethanol were used to wash and filter alternately until the filtered solution was a clear solution. The brown precipitate on the filter paper was placed in an electric blast drying oven and dried at a constant temperature of 80°C for 6 hours. After drying, it was ground into powder to obtain carbon balls;

[0052] Step 2, preparation of Al2O3 hollow spheres: adding 30mmol of aluminum chloride to 120mL of a water-alcohol mixed solution (containing 99% by mass of anhydrous ethanol) and stirring rapidly to dissolve it completely to obtain an aluminum chloride solution, taking 1g of the carbon ball prepared in the step 1 and adding it to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, placing the carbon ball mixed solution in a numerically controlled ultrasonic cleaner for ultrasonic oscillation for 0.6h to uniformly load the aluminum ions on the carbon balls, then taking 0.1mol of urea and adding it to the dispersed carbon ball mixed solution, stirring uniformly in a 70°C water bath for 15h, and filtering with a vacuum filtration pump to obtain a brown solid, washing the brown solid with deionized water and anhydrous ethanol alternately, and then drying it in a blast drying oven, drying it at a constant temperature of 70°C for 8 hours, and calcining the dried brown solid in a muffle furnace at a temperature of 1050°C for 3h to obtain Al2O3 hollow spheres;

[0053] Step 3, preparation of Zr@γ-Al2O3 hollow spheres: the Al2O3 hollow spheres obtained in the step 2 are fully immersed in a zirconium nitrate solution with a mass concentration of 4% for 11 hours, the Zr-loaded Al2O3 hollow spheres are taken out and dried at a constant temperature of 80°C for 6 hours, and calcined at 700°C for 2 hours to obtain finished Zr@γ-Al2O3 hollow spheres.

[0054] like Figure 2 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 80.69%.

[0055] Embodiment 5

[0056] The preparation method of this embodiment is basically the same as that of the first embodiment, except that: the mass concentration of zirconium nitrate in step 3 of this embodiment is 6%, and the mass concentration of water-alcohol mixed solution (containing 25% anhydrous ethanol) in step 2 of this embodiment is 120 mL; and the mass concentration of zirconium nitrate in step 3 of this embodiment is 6%.

[0057] like Figure 3 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 93.85%.

[0058] Embodiment 6

[0059] The preparation method of this embodiment is basically the same as that of the first embodiment, except that: the mass concentration of zirconium nitrate in step 3 of this embodiment is 8%, and the mass concentration of water-alcohol mixed solution in step 2 of this embodiment is 120 mL (containing 50% anhydrous ethanol).

[0060] like Figure 3 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 92.37%.

[0061] Embodiment 7

[0062] The preparation method of this embodiment is basically the same as that of the first embodiment, except that: the mass concentration of zirconium nitrate in step 3 of this embodiment is 10%; the mass concentration of water-alcohol mixed solution in step 2 of this embodiment is 120 mL (containing 75% anhydrous ethanol); and the mass concentration of zirconium nitrate in step 3 of this embodiment is 10%.

[0063] like Figure 3 As shown, the removal rate of carbonyl sulfide by catalytic hydrolysis of Zr@γ-Al2O3 nano hollow sphere hydrolysis catalyst in this embodiment is 92.12%.

[0064] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent structural transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A method for preparing a carbonyl sulfide hollow nanosphere hydrolysis catalyst, characterized in that: The following steps are involved: Step 1, preparing glucose carbon balls: dissolving glucose in distilled water and stirring thoroughly to obtain a glucose solution, taking the completely dissolved glucose solution for hydrothermal reaction, and after the hydrothermal reaction, allowing the solution to cool naturally to room temperature, washing and filtering the solution until the solution becomes clear, drying the precipitate obtained by filtration and grinding it into powder to obtain carbon balls; Step 2, preparing Al2O3 hollow spheres: adding aluminum chloride to a water-alcohol mixed solution and stirring rapidly to completely dissolve the aluminum chloride to obtain an aluminum chloride solution, adding the carbon balls prepared in the step 1 to the aluminum chloride solution and stirring evenly to obtain a carbon ball mixed solution, ultrasonically oscillating the carbon ball mixed solution for 0.5h-1h to load aluminum ions on the carbon balls, then adding urea to the oscillated carbon ball mixed solution, and stirring uniformly in a water bath at 60°C-70°C for 12h-18h, then filtering to obtain a brown solid, washing and drying the brown solid, and then sending it to a muffle furnace for calcination to obtain Al2O3 hollow spheres; Step 3: Prepare Zr@γ-Al2O3 hollow spheres: immerse the Al2O3 hollow spheres obtained in step 2 in a zirconium nitrate solution for 9h-12h, then take out, dry and calcine to obtain finished Zr@γ-Al2O3 hollow spheres, i.e., carbonyl sulfide nano hollow sphere hydrolysis catalysts.

2. The preparation method according to claim 1, characterized in that: The hydrothermal reaction in step 1 is to place the glucose solution in a polytetrafluoroethylene hydrothermal reactor, and then place the reactor in an electric heated blast drying oven to react for 2h-10h at a constant temperature of 150°C-250°C.

3. The preparation method according to claim 2, characterized in that: The drying conditions in steps 1 to 3 are all to dry in a blast drying oven at a constant temperature of 60° C. to 80° C. for 6 h to 12 h.

4. The preparation method according to claim 3, characterized in that: The washing in step 1 and step 2 is specifically washing with deionized water and anhydrous ethanol alternately.

5. The preparation method according to claim 1, characterized in that: The calcination temperature for preparing Al2O3 hollow spheres in step 2 is 650°C-1150°C, and the calcination time is 1h-4h.

6. The preparation method according to claim 5, characterized in that: The calcination temperature for preparing Zr@γ-Al2O3 hollow spheres in step 3 is 400°C-700°C, and the calcination time is 2h-3h.

7. The preparation method according to claim 6, characterized in that: The mass concentration of the zirconium nitrate solution in step 3 is 4%-10%.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The amount of glucose used in the step 1 is 6 g, the amount of distilled water used is 100 mL, and the amount of glucose solution used for the hydrothermal reaction is 70 mL.

9. The preparation method according to claim 8, characterized in that: In the step 2, the amount of aluminum chloride used is 20 mmol-50 mmol, the amount of carbon balls used is 1 g, and the amount of urea used is 0.1 mol.

10. The preparation method according to claim 9, characterized in that: The amount of the water-alcohol mixed solution in step 2 is 120 mL. The water-alcohol mixed solution consists of anhydrous ethanol and water, and the mass of the anhydrous ethanol accounts for 1%-99% of the mass of the water-alcohol mixed solution.

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