CN112371111B

CN112371111B - Preparation method of hollow silica supported confined catalyst and application of hollow silica supported confined catalyst in oxidative desulfurization of fuel oil

Info

Publication number: CN112371111B
Application number: CN202011319802.0A
Authority: CN
Inventors: 蒋伟; 肖进; 高翔; 安鑫; 王超; 朱文帅; 李华明
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2020-11-23
Filing date: 2020-11-23
Publication date: 2023-03-21
Anticipated expiration: 2040-11-23
Also published as: CN112371111A

Abstract

The invention belongs to the technical field of fuel oil desulfurization, and relates to a preparation method of a hollow silicon dioxide supported confinement catalyst, which comprises the following steps: ultrasonically dispersing cetyl trimethyl ammonium bromide and polystyrene microspheres containing molybdenum precursor active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 18-30 h, centrifugally separating, washing and drying; and putting the solid in a muffle furnace, heating to 500-1000 ℃ at the heating rate of 2 ℃/min, calcining for 6-12 h, and naturally cooling to room temperature to obtain the catalyst. The invention also aims to apply the prepared catalyst to the oxidative desulfurization of fuel oil. The method has simple process, the active center of the catalyst is molybdenum oxide, the oxidant is hydrogen peroxide, dibenzothiophene in the oil phase enters the hollow silica spheres through the pore channels of the silica spheres during the reaction and reacts, and the separation of the catalyst and the oil phase is realized. Has the advantages of high desulfurization speed, high efficiency, simple reaction system, mild reaction conditions, good cycle performance and the like.

Description

Preparation method of hollow silica supported confined catalyst and application of hollow silica supported confined catalyst in oxidative desulfurization of fuel oil

Technical Field

The invention belongs to the technical field of fuel oil desulfurization, relates to a desulfurization catalyst, and particularly relates to a preparation method of a hollow silica supported confined catalyst and application of the hollow silica supported confined catalyst to fuel oil oxidative desulfurization.

Background

With the rapid development of human society and the increasing use of fuel oil, sulfur compounds in the fuel oil are combusted to generate sulfur oxides SO _x Not only can harm the catalyst in the automobile engine and the tail gas treatment device, but also can cause adverse effects on human health and natural environment. Due to the increasing emphasis of environmental problems, the removal of sulfide in fuel oil has attracted attention of all countries in the world, and in recent years, all countries have successively issued relevant laws and regulations, and strict limits are made on the sulfide content, and the sulfur content in fuel oil is basically required to be lower than 10ppm. At present, hydrodesulfurization (HDS) is mainly used as a desulfurization method in industry, but the hydrodesulfurization needs high-temperature and high-pressure reaction conditions, the removal rate of sulfur compounds such as p-benzothiophene is not high, and the octane number of an oil product is reduced to a certain extent during actual operation, so that the quality of fuel oil is reduced. Therefore, it is urgently required to find a deep desulfurization technique that replaces HDS. The non-HDS process mainly comprises Extraction Desulfurization (EDS), adsorption Desulfurization (ADS), oxidation Desulfurization (ODS), biological Desulfurization (BDS) and the like, wherein the ODS has high removing efficiency on thiophene sulfur-containing compounds, and the reaction condition is mild, so that the process is considered to be one of the processes with the most research prospects.

Silica itself has many excellent characteristics, such as low price, no toxicity, stable chemical property, controllable structure and the like, and the physical interaction of the silica mainly relates to the internal confinement effect of the hollow silica; the inner and outer mass transfer of the thiophene compound can be selectively carried out by adjusting the pore diameter structure, and the thiophene compound also has good stability. A great deal of literature indicates that the use of transition metal oxide activated hydrogen peroxide for oxidative desulfurization is one of the hot spots of fuel oil desulfurization research at present, but molybdenum oxide (MoO) _x ) The catalyst is loaded in the carrier for oxidative desulfurization, and relatively few researches are carried out.

Disclosure of Invention

In view of the defects in the prior art, the invention aims to provide a preparation method of a hollow silica supported confinement catalyst.

A preparation method of a hollow silica supported confined catalyst comprises the following steps:

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor active ingredients in a pure water solution of ethanol, then adding concentrated ammonia water and tetramethyl silicate, reacting for 18-30 h, preferably 24h, centrifugally separating, washing and drying; putting the solid in a muffle furnace, heating to 500-1000 ℃ at the heating rate of 2 ℃/min, calcining for 6-12 h, preferably 600 ℃ for 10h, naturally cooling to room temperature to obtain the hollow silica supported confinement catalyst, wherein the mass-volume ratio of CTAB, polystyrene containing active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.1-0.5 g: 0.1-0.5 g: 100-200 mL: 50-100 mL: 5-20 mL:1 to 10mL, preferably 0.2g:0.4g:160mL of: 40mL of: 10mL of: 2mL.

In the better disclosed example of the invention, the tetramethyl silicate is added in 5 times with equal amount, and the interval is 30min.

In the better disclosed example of the invention, the mass percentage concentration of the strong ammonia water is 25-28%.

In a preferred embodiment of the present invention, the preparation method of the polystyrene microsphere containing the molybdenum precursor as the active component comprises the following steps: (1) Synthesis of positively charged modified polystyrene

Styrene is dispersed in water after passing through an alkaline alumina column, nitrogen is introduced, azodiisobutyl amidine hydrochloride (AIBA) is added, and the mixture is stirred and reacted for 0.5 to 4 hours at the temperature of between 80 and 120 ℃, and preferably reacted for 1 hour at the temperature of 95 ℃; continuously adding 2- (methacryloyl) -ethyltrimethyl ammonium chloride (MTC), equal amount of styrene and water, reacting for 18-30 h, preferably 23h, centrifugally separating, washing with ethanol and drying to obtain the modified polystyrene microsphere with positive charge, wherein the mass-volume ratio of AIBA, MTC, styrene to water is 0.1-0.5 g: 0.1-0.5 g: 2-5 g:50 to 200mL, preferably 0.1g:0.2g:2.5g:100mL;

(2) Synthesis of polystyrene with active material by ion exchange method

Ultrasonically dispersing the modified polystyrene microspheres in water to obtain a dispersion, and then performing isovolumetric ion exchange with a molybdenum-containing precursor aqueous solution to obtain polystyrene microspheres containing active ingredients, wherein the mass ratio of the modified polystyrene microspheres to phosphomolybdic acid is (0.3-1 g): 0.005 to 0.1g, preferably 0.5g:0.008g.

In a preferred embodiment of the present invention, the molybdenum-containing precursor in step (2) is a molybdenum-containing lewis acid or phosphomolybdic acid, ammonium molybdate, or sodium molybdate, preferably phosphomolybdic acid.

According to the method, the prepared hollow silica supported confined catalyst takes the hollow silica as a carrier, and molybdenum oxide is uniformly dispersed on the inner wall of the hollow silica.

The invention also aims to apply the prepared hollow silica supported confinement catalyst to the oxidative desulfurization of fuel oil.

The method specifically comprises the following steps: the prepared catalyst MoO _x Putting the/HS into model oil, adding hydrogen peroxide, stirring and reacting at a certain temperature, and separating an upper oil phase after the reaction is finished, wherein the upper oil phase is the desulfurized oil product; and analyzing the sulfur content in the model oil by using gas chromatography, and calculating the desulfurization rate.

The catalyst MoO _x in/HS, moO _x Can activate hydrogen peroxide.

The dosage ratio of the catalyst to the model oil is 0.005-0.05 g: 5-20 mL, the model oil contains aliphatic sulfide or aromatic sulfide, and the sulfur content is 10-1000ppm.

The molar ratio of the hydrogen peroxide to the model oil is 2-8.

In the reaction, the stirring speed is 400-1000 rpm, the reaction temperature is 30-80 ℃, and the reaction time is 60-120 min.

The desulfurization rate calculation formula is as follows:

the catalyst prepared by the invention can be used for removing aliphatic sulfides and aromatic sulfides in oil products by catalytic oxidation, such as Dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-DMDBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT), wherein the oxidation reaction of Dibenzothiophene (DBT) and hydrogen peroxide can be expressed by an equation as follows:

the catalyst prepared by the invention adopts hydrogen peroxide as an oxidant, has high sulfur compound removal rate and high efficiency, and can meet the requirement of deep desulfurization under the optimal reaction condition; the reaction condition is mild, no pressurizing equipment is needed, and the operation is simple, convenient and safe; after the reaction is finished, the catalyst and the reaction system are easy to separate, the separation is realized by standing or centrifuging, the catalyst can be recycled, other toxic byproducts are not generated in the reaction, and the method is harmless to the environment; the catalyst has excellent cycle performance, the activity is basically kept unchanged after several cycles of use, and ultra-deep desulfurization can still be realized; the catalyst adopts hollow silicon dioxide spheres to active substances (MoO) _x ) The encapsulation is carried out, and the loss of active substances in the using process is prevented to the maximum extent.

Advantageous effects

The preparation method disclosed by the invention has the advantages that the process is simple, the carrier of the catalyst is hollow silicon dioxide, the active center is molybdenum oxide, the oxidant is hydrogen peroxide, during the reaction, dibenzothiophene in the oil phase enters the hollow silicon dioxide ball through the pore channel of the silicon dioxide ball for reaction, and the separation of the catalyst and the oil phase can be realized after the reaction is finished. The catalyst has the advantages of high activity and good cycle performance of the supported catalyst. Compared with the traditional desulfurization method, the method has the advantages of high desulfurization rate, high efficiency, simple reaction system, mild reaction conditions, good cycle performance and the like.

Drawings

FIG. 1 is a transmission electron micrograph of a catalyst;

FIG. 2 XPS plot of catalyst;

FIG. 3. Cycle performance testing of the catalyst, showing that the catalyst can be cycled 6 times;

FIG. 4 is a GC-MS graph of model oil before reaction (DBT as sulfur compound concentration 200ppm, hexadecane as internal standard, concentration 4000 ppm);

FIG. 5 GC-MS plot of model oil after reaction (DBT as sulfur compound concentration 200ppm, hexadecane as internal standard, concentration 4000 ppm).

Detailed Description

The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.

The preparation method of the polystyrene microsphere containing the active ingredients comprises the following steps:

(1) firstly, styrene passes through an alkaline alumina column, 100mL of water and 2.5g of styrene are added into a three-neck flask, nitrogen is introduced for 10min, 0.1g of azodiisobutyl amidine hydrochloride (AIBA) is added, stirring reaction is carried out at 95 ℃ for 1h, then 0.2g of 2- (methacryloyl) -ethyltrimethyl ammonium chloride (MTC), 2.5g of styrene and 100mL of water are added, reaction is continued for 23h, reaction products are centrifugally separated, washed by ethanol and dried, and modified polystyrene microspheres can be obtained;

(2) ultrasonically dispersing 0.05g of modified polystyrene microsphere in 20mL of water to obtain a dispersion solution, dissolving 0.008g of phosphomolybdic acid in 20mL of water, performing ion exchange, and separating and drying to obtain the polystyrene microsphere containing the active ingredient.

Preparing a model oil product: dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) are respectively dissolved in dodecane, and the sulfur content of an oil prepared from DBT is 10-1000ppm, the sulfur content of an oil prepared from 4-MDBT is 10-1000ppm, and the sulfur content of an oil prepared from 4,6-DMDBT is 10-1000ppm.

Example 1

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor (phosphomolybdic acid) active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 18h, centrifugally separating, washing and drying; and placing the solid in a muffle furnace, calcining at the heating rate of 2 ℃/min and the temperature of 600 ℃ for 10h, and naturally cooling to room temperature to obtain the hollow silica supported limited-domain catalyst, wherein the mass-volume ratio of CTAB, polystyrene containing active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.4g:0.1g:160mL of: 40mL of: 10mL of: 5mL; the tetramethyl silicate is added for 5 times at intervals of 30min.

The successful synthesis of a hollow supported catalyst can be seen from figure 1;

the high resolution peak separation spectrum of molybdenum from FIG. 2 shows the presence of two sets of signal peaks, 233.78eV and 236.98eV,232.47eV and 233.59eV, indicating MoO _x The existence of the catalyst can successfully synthesize the molybdenum catalyst containing different valence states.

The conversion of DBT to DBTO in the reacted oil is clearly seen in conjunction with FIGS. 4-5 ₂ 。

Example 2

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor (ammonium molybdate) active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 24h, centrifugally separating, washing and drying; and placing the solid in a muffle furnace, calcining at the temperature rising rate of 4 ℃/min and 800 ℃ for 5h, and naturally cooling to room temperature to obtain the hollow silica supported limited-domain catalyst, wherein the mass-volume ratio of CTAB, polystyrene containing active components, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.1g:0.3g:100mL of: 100mL of: 5mL of: 1mL; the tetramethyl silicate is added for 5 times at intervals of 30min.

Example 3

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor (sodium molybdate) active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 27h, centrifugally separating, washing and drying; and placing the solid in a muffle furnace, calcining at the heating rate of 3 ℃/min and the temperature of 700 ℃ for 6h, and naturally cooling to room temperature to obtain the hollow silica supported limited-domain catalyst, wherein the mass-volume ratio of CTAB, polystyrene containing active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.2g:0.2g:120mL of: 80mL of: 7mL of: 3mL; the tetramethyl silicate is added for 5 times at intervals of 30min.

Example 4

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor (potassium molybdate) active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 30h, centrifugally separating, washing and drying; and placing the solid in a muffle furnace, calcining at the heating rate of 1 ℃/min and the temperature of 500 ℃ for 9h, and naturally cooling to room temperature to obtain the hollow silica supported limited-domain catalyst, wherein the mass-volume ratio of CTAB, polystyrene containing active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.3g:0.5g:70mL of: 130mL of: 8mL of: 6mL; the tetramethyl silicate is added for 5 times at intervals of 30min.

Example 5

ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor (phosphomolybdic acid) active ingredients in an ethanol solution, then adding concentrated ammonia water and tetramethyl silicate, reacting for 20h, centrifugally separating, washing and drying; and placing the solid in a muffle furnace, calcining at the temperature rising rate of 4 ℃/min and the temperature rising rate of 1000 ℃ for 7h, and naturally cooling to room temperature to obtain the hollow silica supported confinement catalyst, wherein the mass-to-volume ratio of CTAB, polystyrene containing active components, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.5g:0.4g:50mL of: 90mL of: 20mL of: 5mL; the tetramethyl silicate is added for 5 times at intervals of 30min.

The catalyst prepared in the above examples was subjected to a simulated desulfurization test, which is described in detail in the following examples.

Experimental example 1

5mL of model oil of DBT, 4-MDBT and 4,6-DMDBT (sulfur content of oil is 200ppm, 500ppm and 1000ppm respectively) was added into three customized water bath flasks, 0.005g of the prepared catalyst (calcined at 600 ℃ for 10h, heating rate 2 ℃/min, phosphomolybdic acid loading of 1%) and oxygen-sulfur ratio of 6 were added, the mixture was magnetically stirred at 600rpm for 90min at 50 ℃ to separate out the model oil, and the DBT, 4-MDBT and 4,6-DMDBT contents in the oil were respectively detected by GC-FID (internal standard method, hexadecane as an internal standard, and internal standard concentration of 4000 ppm), and the sulfur removal rates were respectively 99.8%, 99.7% and 44.0% by calculation.

Experimental example 2

Adding 10mL of DBT model oil (the sulfur content of an oil product is 600 ppm) into four customized water bath jacketed bottles, then adding 0.01g of the prepared catalyst (calcining for 5 hours at 800 ℃ under the air condition, the heating rate is 4 ℃/min, the phosphomolybdic acid loading is 5 percent), the oxygen-sulfur ratio is 4, magnetically stirring for 120min at 800rpm at 30 ℃, 50 ℃, 60 ℃ and 80 ℃ respectively, separating out the model oil, detecting the DBT content in the oil by adopting GC-FID (internal standard method, hexadecane is used as an internal standard substance, and the concentration of the internal standard is 4000 ppm) respectively, and calculating the sulfur removal rate to be 9.3%, 91.1%, 99.8% and 99.8% respectively.

Experimental example 3

20mL of DBT model oil (sulfur content of oil is 400 ppm) was added to three-necked flasks, followed by 0.02g of the above prepared catalyst (calcined at 700 ℃ for 6h under nitrogen, heating rate of 3 ℃/min, phosphomolybdic acid loading of 10%) and oxygen-to-sulfur ratio of 2,5 and 8, respectively, magnetic stirring at 500rpm at 40 ℃ for 100min to separate the model oil, GC-FID (internal standard method, hexadecane as internal standard, concentration of internal standard of 4000 ppm) was used to detect DBT content in the oil, and sulfur removal rates were calculated to be 98.7%, 99.8% and 99.7%, respectively.

Experimental example 4

Adding 15mL of DBT model oil (the sulfur content of an oil product is 800 ppm) into four customized water bath jacketed bottles, adding p-xylene, toluene, cyclohexane and cyclohexene (485 muL, 480 muL, 515 muL and 510 muL) with the mass ratio of 10 percent of DBT, then adding 0.03g of the prepared catalyst (calcining for 9 hours at 500 ℃ under the condition of nitrogen, the heating rate is 1 ℃/min, the load of phosphomolybdic acid is 20 percent), and magnetically stirring for 80 minutes at 600rpm at 70 ℃ with the oxygen-sulfur ratio of 3 to separate out the model oil, detecting the DBT content in the oil by adopting GC-FID (internal standard method, hexadecane is used as an internal standard substance, and the concentration of the internal standard is 4000 ppm), and calculating the sulfur removal rates to be 98.7 percent, 98.9 percent, 99.3 percent and 95.9 percent respectively.

Experimental example 5

5mL of DBT model oil (the sulfur content of the oil is 1000 ppm) was added to four custom water-bath flasks, 0.05g of the catalyst prepared above (calcined at 1000 ℃ for 7h under nitrogen, the temperature rise rate is 4 ℃/min, the phosphomolybdic acid loading is 8%), the oxygen-sulfur ratio is 8, and the catalyst was magnetically stirred at 50 ℃ and 700rpm for 30min, 60min, 90min and 120min, respectively, to separate the model oil, the DBT content in the oil was determined by GC-FID (internal standard method), and the sulfur removal rates were calculated to be 74.9%, 98.2%, 99.8% and 99.9%, respectively.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims

1. A preparation method of a hollow silica supported limited-area catalyst applied to fuel oil oxidation desulfurization is characterized by comprising the following steps: ultrasonically dispersing Cetyl Trimethyl Ammonium Bromide (CTAB) and polystyrene microspheres containing molybdenum precursor active ingredients into a pure water solution of ethanol, then adding concentrated ammonia water and tetramethyl silicate, reacting for 18-30 h, centrifugally separating, washing and drying; placing the solid in a muffle furnace, heating to 500-1000 ℃ at the heating rate of 2 ℃/min, calcining for 6-12 h, naturally cooling to room temperature, and obtaining the hollow silica supported confinement catalyst, wherein the mass-volume ratio of CTAB, polystyrene microspheres containing molybdenum precursor active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.1-0.5 g: 0.1-0.5 g: 100-200 mL: 50-100 mL: 5-20 mL: 1-10 mL;

the preparation method of the polystyrene microsphere containing the molybdenum precursor active component comprises the following steps:

(1) Dispersing styrene in water after passing through an alkaline alumina column, introducing nitrogen, adding azodiisobutyl amidine hydrochloride AIBA, stirring at 80-120 ℃ for reaction for 0.5-4 h, continuously adding 2- (methacryloyl) -ethyltrimethyl ammonium chloride MTC, equal amount of styrene and water, reacting for 18-30 h, centrifugally separating, washing with ethanol and drying to obtain the modified polystyrene microsphere with positive charge, wherein the mass-volume ratio of AIBA, MTC, styrene to water is 0.1-0.5 g: 0.1-0.5 g: 2-5 g: 50-200 mL;

(2) Ultrasonically dispersing modified polystyrene microspheres in water to obtain a dispersion, and then performing isovolumetric ion exchange with a molybdenum-containing precursor aqueous solution to obtain polystyrene microspheres containing active ingredients, wherein the mass ratio of the modified polystyrene microspheres to the molybdenum-containing precursor is 0.3-1 g: 0.005-0.1 g.

2. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: the tetramethyl silicate is added in 5 times at an interval of 30min.

3. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: the mass percentage concentration of the strong ammonia water is 25-28%.

4. The preparation method of the hollow silica supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized by comprising the following steps: adding concentrated ammonia water and tetramethyl silicate, and reacting for 24h.

5. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: and putting the solid in a muffle furnace, and heating to 600 ℃ at a heating rate of 2 ℃/min for calcining for 10h.

6. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: the mass volume ratio of CTAB, polystyrene microspheres containing molybdenum precursor active components, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.2g:0.4g:160mL of: 40mL of: 10mL of: 2mL.

7. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: and (2) after the styrene passes through the basic alumina column in the step (1), dispersing the styrene in water, introducing nitrogen, adding azodiisobutyl amidine hydrochloride AIBA, and reacting for 1h at 95 ℃.

8. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: and (2) continuously adding 2- (methacryloyl) -ethyltrimethyl ammonium chloride (MTC), equal amount of styrene and water in the step (1), reacting for 23h, performing centrifugal separation, washing with ethanol and drying.

9. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: in the step (1), the mass-to-volume ratio of AIBA, MTC, styrene and water is 0.1g:0.2g:2.5g:100mL.

10. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: in the step (2), the mass ratio of the modified polystyrene microspheres to the molybdenum-containing precursor is 0.5g:0.008g.

11. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: in the step (2), the molybdenum-containing precursor is Lewis acid containing molybdenum.

12. The preparation method of the hollow silica-supported confinement catalyst applied to the oxidative desulfurization of fuel oil according to claim 1, characterized in that: in the step (2), the molybdenum-containing precursor is phosphomolybdic acid, ammonium molybdate and sodium molybdate.

13. A hollow silica supported constrained-domain catalyst prepared according to the process of any one of claims 1 to 12.

14. The hollow silica supported constrained-bed catalyst of claim 13, wherein: hollow silicon dioxide is used as a carrier, and molybdenum oxide is uniformly dispersed on the inner wall of the hollow silicon dioxide.

15. Use of a catalyst as claimed in any one of claims 13 or 14, wherein: the method is applied to the oxidation desulfurization of fuel oil.