CN112371111A - Preparation method of hollow silica supported confined catalyst and application of hollow silica supported confined catalyst in oxidative desulfurization of fuel oil - Google Patents
Preparation method of hollow silica supported confined catalyst and application of hollow silica supported confined catalyst in oxidative desulfurization of fuel oil Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/28—Molybdenum
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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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 (3) putting the solid in a muffle furnace, heating to 500-1000 ℃ at a 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
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 SOxNot 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 10 ppm. 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 transition metal oxide activated hydrogen peroxide is used for oxidative dehydrogenationSulfur is currently one of the hot spots for fuel oil desulfurization research, 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; placing the solid in a muffle furnace, heating to 500-1000 ℃ at a 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 limited-area 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: 1-10 mL, preferably 0.2 g: 0.4 g: 160mL of: 40mL of: 10mL of: 2 mL.
In the better disclosed example of the invention, the tetramethyl silicate is added in 5 times with equal amount, and the interval is 30 min.
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
Dispersing styrene in water after passing through an alkaline alumina column, introducing nitrogen, adding azodiisobutyl amidine hydrochloride (AIBA), and reacting at 80-120 ℃ for 0.5-4 h with stirring, preferably at 95 ℃ for 1 h; continuously adding 2- (methacryloyl) -ethyltrimethyl ammonium chloride (MTC), styrene and water in equal amount, 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-to-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, preferably 0.1 g: 0.2 g: 2.5 g: 100 mL;
(2) synthesis of polystyrene with active material by ion exchange method
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 phosphomolybdic acid is (0.3-1 g): 0.005-0.1 g, preferably 0.5 g: 0.008 g.
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 confinement 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 MoOxPutting 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 MoOxin/HS, MoOxCan 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 10-1000 ppm.
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 the following equation:
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) Encapsulation is performed to prevent loss of active material to the maximum extent during use.
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:
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 0.05g of modified polystyrene microsphere is ultrasonically dispersed in 20mL of water to obtain dispersion, 0.008g of phosphomolybdic acid is dissolved in 20mL of water for ion exchange, and the polystyrene microsphere containing active ingredients is obtained after separation and drying.
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 10-1000 ppm.
Example 1
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 (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 0.4 g: 0.1 g: 160mL of: 40mL of: 10mL of: 5 mL; the tetramethyl silicate is added for 5 times at intervals of 30 min.
The successful synthesis of a hollow supported catalyst can be seen from figure 1;
the high resolution peak separation spectrum of molybdenum in FIG. 2 shows the existence of two sets of signal peaks of 233.78eV and 236.98eV, 232.47eV and 233.59eV, which indicates that MoOxThe 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. 4-52。
Example 2
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 (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 0.1 g: 0.3 g: 100mL of: 100mL of: 5mL of: 1 mL; the tetramethyl silicate is added for 5 times at intervals of 30 min.
Example 3
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 (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 0.2 g: 0.2 g: 120mL of: 80mL of: 7mL of: 3 mL; the tetramethyl silicate is added for 5 times at intervals of 30 min.
Example 4
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 (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 0.3 g: 0.5 g: 70mL of: 130mL of: 8mL of: 6 mL; the tetramethyl silicate is added for 5 times at intervals of 30 min.
Example 5
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 (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 0.5 g: 0.4 g: 50mL of: 90mL of: 20mL of: 5 mL; the tetramethyl silicate is added for 5 times at intervals of 30 min.
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
Adding 5mL of model oil of DBT, 4-MDBT and 4,6-DMDBT (the sulfur content of oil products is 200ppm, 500ppm and 1000ppm respectively), adding 0.005g of the prepared catalyst (calcining for 10h at 600 ℃, the heating rate is 2 ℃/min, the phosphomolybdic acid loading is 1 percent and the oxygen-sulfur ratio is 6), magnetically stirring for 90min at 600rpm at 50 ℃, separating out the model oil, and respectively detecting the DBT, 4-MDBT and 4,6-DMDBT contents 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 4000ppm), wherein the sulfur removal rates are respectively 99.8%, 99.7% and 44.0% by calculation.
Experimental example 2
10mL of DBT model oil (the sulfur content of the oil is 600ppm) is added into four customized water bath jacketed bottles, then 0.01g of the prepared catalyst (calcined for 5h at 800 ℃ under the air condition, the heating rate is 4 ℃/min, the phosphomolybdic acid loading is 5 percent) and the oxygen-sulfur ratio is 4 are added, the model oil is separated by magnetic stirring at 800rpm at 30 ℃, 50 ℃, 60 ℃ and 80 ℃ for 120min respectively, the DBT content in the oil is detected by adopting GC-FID (internal standard method, hexadecane is used as an internal standard substance, and the concentration of the internal standard substance is 4000ppm), and the sulfur removal rates are respectively 9.3%, 91.1%, 99.8% and 99.8% by calculation.
Experimental example 3
20mL of DBT model oil (the sulfur content of the oil is 400ppm) was added to three-necked flasks, followed by 0.02g of the catalyst prepared above (calcined at 700 ℃ C. under nitrogen for 6 hours, with a heating rate of 3 ℃/min, a phosphomolybdic acid loading of 10%) and an oxygen-to-sulfur ratio of 2, 5 and 8, respectively, and magnetically stirred at 40 ℃ for 100min at 500rpm to isolate the model oil, the DBT content in the oil was measured by GC-FID (internal standard method, hexadecane as an internal standard, and the concentration of the internal standard was 4000ppm), and the 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 800ppm) 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 4000ppm), 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 1000ppm) 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 (9)
1. A preparation method of a hollow silica supported confined catalyst 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 a 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 limited-area 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: 1-10 mL.
2. The method for preparing the hollow silica supported constrained-domain catalyst according to claim 1, wherein: the tetramethyl silicate is added in 5 times at an interval of 30 min.
3. The method for preparing the hollow silica supported constrained-domain catalyst according to claim 1, wherein: the mass percentage concentration of the strong ammonia water is 25-28%.
4. The method for preparing the hollow silica supported constrained-domain catalyst according to claim 1, wherein: adding concentrated ammonia water and tetramethyl silicate, and reacting for 24 h.
5. The method for preparing the hollow silica supported constrained-domain catalyst according to claim 1, wherein: and putting the solid in a muffle furnace, and heating to 600 ℃ at the heating rate of 2 ℃/min for calcining for 10 h.
6. The method for preparing the hollow silica supported constrained-domain catalyst according to claim 1, wherein: the mass volume ratio of CTAB, polystyrene containing active ingredients, ethanol, pure water, concentrated ammonia water and tetraethyl silicate is 0.2 g: 0.4 g: 160mL of: 40mL of: 10mL of: 2 mL.
7. A hollow silica supported constrained-bed catalyst prepared according to the process of any one of claims 1 to 6.
8. The hollow silica supported constrained-bed catalyst of claim 7, wherein: hollow silicon dioxide is used as a carrier, and molybdenum oxide is uniformly dispersed on the inner wall of the hollow silicon dioxide.
9. Use of a catalyst according to any of claims 7 or 8, wherein: the method is applied to the oxidation desulfurization of fuel oil.
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| CN113499782A (en) * | 2021-07-30 | 2021-10-15 | 江苏大学 | Preparation of hollow mesoporous silica dissolved regeneration limited-area cobalt molybdate catalyst and catalytic oxidation diesel oil desulfurization method |
| CN113509959A (en) * | 2021-08-03 | 2021-10-19 | 重庆邮电大学 | Preparation method of hollow mesoporous nano silicon spheres for packaging chiral catalyst, product and application thereof |
| CN114308134A (en) * | 2022-01-11 | 2022-04-12 | 北京科技大学 | Method for preparing metal oxide microreactor by using halloysite nanotubes and application of method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113499782A (en) * | 2021-07-30 | 2021-10-15 | 江苏大学 | Preparation of hollow mesoporous silica dissolved regeneration limited-area cobalt molybdate catalyst and catalytic oxidation diesel oil desulfurization method |
| CN113499782B (en) * | 2021-07-30 | 2024-03-01 | 江苏大学 | Preparation method of hollow mesoporous silica dissolution regeneration limited-domain cobalt molybdate catalyst and catalytic oxidation diesel desulfurization method |
| CN113509959A (en) * | 2021-08-03 | 2021-10-19 | 重庆邮电大学 | Preparation method of hollow mesoporous nano silicon spheres for packaging chiral catalyst, product and application thereof |
| CN114308134A (en) * | 2022-01-11 | 2022-04-12 | 北京科技大学 | Method for preparing metal oxide microreactor by using halloysite nanotubes and application of method |
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| CN112371111B (en) | 2023-03-21 |
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