CN110833867B - Preparation method and desulfurization application of three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst - Google Patents
Preparation method and desulfurization application of three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 64
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 29
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
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- 239000000295 fuel oil Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- NFKMSYOEMWGTMW-UHFFFAOYSA-N 5-sulfanylidenedibenzothiophene Chemical class C1=CC=C2S(=S)C3=CC=CC=C3C2=C1 NFKMSYOEMWGTMW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
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- 239000000203 mixture Substances 0.000 claims description 11
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- 150000001875 compounds Chemical class 0.000 description 7
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- 238000001816 cooling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
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- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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- 150000003681 vanadium Chemical class 0.000 description 1
- 238000000193 wide-angle powder X-ray diffraction Methods 0.000 description 1
Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention belongs to the technical field of material preparation and catalytic reaction, and relates to a preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst, which is prepared by mixing vanadium-based ionic liquid [ (C)nH2n+1)3NCH3]3H3V10O28And 3D g-C3N4Respectively dispersing the two into absolute ethyl alcohol with the same volume, fully stirring and mixing the two to carry out a solvothermal reaction, wherein the solvothermal reaction temperature is 100-150 ℃, and the solvothermal reaction time is 12-36 hours; and drying the separated product to obtain the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst. Also discloses the application of the prepared catalyst in the field of catalytic oxidation desulfurization. According to the invention, the three-dimensional porous carbon nitride with rich pore structures is prepared by regulating and controlling the raw material ratio of the prepared three-dimensional porous carbon nitride, and is used as a carrier to load vanadium-based ionic liquid, so that the ionic liquid is favorably placed and highly dispersed. Air is used as an oxidant in the oxidation desulfurization process, and the oxidation desulfurization process is environment-friendly. The obtained supported catalyst combines adsorption and oxidative desulfurization, and can efficiently remove dibenzothiophene sulfides in fuel oil.
Description
Technical Field
The invention belongs to the technical field of material preparation and catalytic reaction, relates to catalytic oxidation desulfurization, and particularly relates to a preparation method and desulfurization application of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst.
Background
Sulfur compounds in fuel oil, if not effectively treated, can produce sulfur oxides such as SO after combustion2、SO3And the like, causing serious environmental pollution. With the gradual enhancement of environmental awareness, environmental regulations become stricter, China already executes the national VI standard of vehicle fuel oil, and the sulfur content in the fuel oil is required to be not more than 10 ppm, which puts higher requirements on the fuel oil desulfurization process. Although the hydrodesulfurization process used in industry can achieve this object, it is very demanding in terms of the desulfurization process conditions for Dibenzothiophene (DBT) sulfides and is costly. Therefore, catalytic oxidation desulfurization techniques have been attracting attention.
The supported catalyst is used as a kind of heterogeneous catalyst and is widely applied to the oxidation desulfurization process. Wherein, the graphite-like phase carbon nitride (g-C)3N4) Is a cheap and easily synthesized non-metallic material, and is often selected as a carrier to prepare a supported catalyst. However, block g-C3N4The specific surface area is usually small, which is not beneficial to effective dispersion of active ingredients, and the adsorption performance to DBT sulfides is not good, if the carbon nitride with a porous structure can be prepared, the specific surface area of the carrier carbon nitride can be greatly improved, and the adsorption performance to DBT sulfides can also be improved. In addition, the common oxidant in oxidative desulfurization is hydrogen peroxide, certain transportation cost is required in the using process, and explosion risks exist. Therefore, development of more environmentally friendly oxidants is needed to perfect the catalytic oxidation desulfurization process.
The invention can prepare the three-dimensional porous carbon nitride (3D g-C) with larger specific surface area by screening cheap and easily-obtained raw materials to carry out supramolecular assembly and carrying out thermal polycondensation through high-temperature roasting treatment3N4) It is an ideal carrier for oxidation desulfurization process. The supported vanadium-based ionic liquid catalyst can be constructed by combining the vanadium-based ionic liquid synthesized by an ion exchange method and the carrier. The catalyst can efficiently oxidize and remove DBT sulfides in fuel oil by taking air as an oxidant, so that the oxidative desulfurization process is more environment-friendly and has better application prospect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst to obtain a supported catalyst.
The technical scheme is as follows:
a preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst comprises the following steps:
mixing vanadium-based ionic liquid [ (C)nH2n+1)3NCH3]3H3V10O28(abbreviated as C)nV10O28) And 3D g-C3N4Respectively dispersing in absolute ethyl alcohol with the same volume, wherein the vanadium-based ionic liquid CnV10O28And 3D g-C3N4The mass-to-volume ratio of the absolute ethyl alcohol to the absolute ethyl alcohol is 0.01-0.04 g: 0.06-0.09 g: 15-20 mL, the absolute ethyl alcohol and the absolute ethyl alcohol are fully stirred, mixed and transferred to a reaction kettle lined with temperature-resistant and acid-resistant bricks and lined with polytetrafluoroethylene for solvothermal reaction, the solvothermal reaction temperature is 100-150 ℃, and the solvothermal reaction time is 12-36 hours; drying the separated product at 80-120 ℃ for 1-8 h to obtain the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst, which is expressed as X-CnV10O28/3D g-C3N4Wherein X represents the loading of the vanadium-based ionic liquid.
In the preferred embodiment of the invention, the vanadium-based ionic liquid CnV10O28Wherein the cationic carbon chain length n = 2,4, 8.
In the preferred embodiment of the invention, the vanadium-based ionic liquid CnV10O28And 3D g-C3N4And the mass-to-volume ratio of the absolute ethyl alcohol is 0.02g to 0.08g to 20 mL.
In the preferred embodiment of the invention, the time for fully stirring the mixture is 0.5-2 h.
In the preferred embodiment of the invention, the solvothermal reaction temperature is 100 ℃ and the time is 24 hours.
In the preferred embodiment of the invention, the drying temperature of the product is 100 ℃ and the time is 6 hours.
The preparation method of the vanadium-based ionic liquid comprises the following steps:
under the condition of oil bath at 60 ℃, 4.5 g of sodium metavanadate is dissolved in 25 mL of deionized water; adding 6.2 mL of 1.5 mol/L phosphoric acid, adjusting the pH to 5.5 by using 1.5 mol/L nitric acid, and violently stirring to obtain a black-red solution; slowly adding 0.54 g of KCl, cooling to room temperature, and precipitating orange yellow crystal K3H3V10O28Filtering and drying the product; 1.1 g K3H3V10O28(1 mmol) was dissolved in 25 mL hydrochloric acid (1 mol/L) in a 60 ℃ oil bath, the pH was adjusted to 5.5 with deionized water, and 6 mL [ (C) was added dropwisenH2n+1)3NCH3]A solution of Cl (TnCl, n = 2,4,8, 3 mmol) in absolute ethanol with solid formation, stirring for 2 h; filtering and separating the obtained solid, and vacuum drying at 60 ℃ for 24h to obtain the vanadium-based ionic liquid CnV10O28Where n = 2,4, 8.
3D g-C of the invention3N4The preparation method comprises the following steps:
taking 0.02 mol of melamine, mixing the three raw materials according to the molar ratio of melamine to cyanuric acid to urea of 1:1: x, wherein x = 1/3, 1/2, 1, 2 and 3, dissolving the mixture in 80 mL of ethanol, stirring for 3 h, and then carrying out ultrasonic treatment for 3 h; then the suspension is opened and stirred in an oil bath at 60 ℃ until no obvious liquid exists, and then the suspension is placed in a drying oven at 60 ℃ to be dried to obtain white powder; placing white powder in a temperature programmed tube furnace, heating to 550 deg.C at a heating rate of 2 deg.C/min in nitrogen atmosphere, maintaining for 4h, and cooling to room temperature to obtain light yellow 3D g-C3N4And (3) powder.
The invention also aims to disclose the application of the supported catalyst prepared by the method in the field of catalytic oxidation desulfurization, in particular to the high-efficiency oxidation removal of dibenzothiophene sulfides in fuel oil by taking air as an oxidant.
The block g-C is prepared by the traditional method3N4Disclosure of the inventionThe specific surface area is often small, which is not favorable for high dispersion of active ingredients when used as a carrier, and the adsorption performance to DBT is poor. The invention utilizes a supermolecular assembly method to prepare 3D g-C with rich pore structure3N4The specific surface area of the carbon nitride is greatly improved, high dispersion of active ingredients is facilitated, and the adsorption performance of the carrier on sulfur-containing compounds is enhanced. The synthesized vanadium-based ionic liquid has the performance of activating air oxidation desulfurization, so that the oxidation desulfurization process is more environment-friendly, the air source is wide, and the oxidation desulfurization cost can be further reduced.
The composition and morphology of the product were analyzed by infrared spectroscopy (FT-IR), wide-angle X-ray powder diffraction (XRD), scanning electron microscope (SWM), Transmission Electron Microscope (TEM), and the like. DBT is taken as a typical sulfur-containing compound to prepare model oil, air is taken as an oxidant, and the synthesized supported vanadium-based ionic liquid catalyst is applied to oxidative desulfurization. The catalytic performance of the supported catalyst was evaluated by detecting the amount of DBT remaining in the model oil after the reaction by a Gas Chromatograph (GC).
The invention prepares the vanadium-based ionic liquid C by using an ion exchange methodnV10O28(n = 2,4, 8) and acts as an active center for the oxidative desulfurization of activated air. The method comprises the steps of carrying out supramolecular assembly by using melamine, cyanuric acid and urea as raw materials, and obtaining 3D g-C by adjusting the mixture ratio of the raw materials and controlling the conditions of thermal polycondensation3N4And acts as a carrier. And mixing the two, and carrying out a solvothermal reaction to obtain the supported vanadium-based ionic liquid catalyst with highly dispersed active ingredients and a stable structure. 3D g-C3N4The adsorption performance of the vanadium-based ionic liquid on DBT is combined with the oxidation performance of the vanadium-based ionic liquid on DBT, so that sulfides in oil products are removed through high-efficiency oxidation, and the aim of deep desulfurization is fulfilled.
Advantageous effects
The invention prepares the three-dimensional porous carbon nitride with rich pore structure by a supermolecule assembly method, designs and synthesizes a series of vanadium-based ionic liquids, combines the vanadium-based ionic liquids and the vanadium-based ionic liquids by a solvothermal method to obtain the supported catalyst, and can use air as an oxidant to ensure that the oxidative desulfurization process is more environment-friendly. Meanwhile, the invention combines adsorption and oxidation desulfurization, the desulfurization efficiency is high, and the supported catalyst can be recycled for multiple times.
Drawings
FIG. 1 FT-IR spectrum of catalyst;
FIG. 2. Wide-angle XRD spectrum of catalyst;
FIG. 3 SEM and TEM photographs of the catalyst;
FIG. 4 is a graph of catalytic oxidative removal performance for different sulfur-containing substrates.
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.
4.5 g of sodium metavanadate was dissolved in 25 mL of deionized water under an oil bath condition at 60 ℃. Adding 6.2 mL of phosphoric acid (1.5 mol/L), adjusting the pH value to 5.5 by nitric acid (1.5 mol/L), and violently stirring to obtain a black red solution (the stirring paddle base material used in the stirring process is a carbon steel material of natural rubber as an external wrapping object, and the whole is vulcanized at high temperature, so that the stirring paddle base material has strong corrosion resistance on nitric acid, phosphoric acid and the like after being vulcanized). Then slowly adding 0.54 g of KCl, cooling to room temperature, and separating out orange yellow crystal K3H3V10O28The product was filtered and dried. 1.1 g K3H3V10O28Dissolved in 25 mL of hydrochloric acid (1 mol/L) in an oil bath at 60 ℃, adjusted to pH 5.5 with deionized water, and added dropwise to 6 mL of [ (C)8H17)3NCH3]Cl（T8Cl, 1.21 g, 3 mmol) in ethanol, an orange-yellow solid formed, and stirring was continued for 2 h. Filtering and separating the obtained orange-yellow solid, and vacuum drying at 60 deg.C for 24h to obtain vanadium-based ionic liquid [ (C)8H17)3NCH3]3H3V10O28。
Melamine, cyanuric acid and urea are used as raw materials, the three raw materials are mixed according to the molar ratio of 1:1:3, then the mixture is dissolved in 80 mL ethanol, and the mixture is subjected to room temperatureStirred for 3 h and sonicated for 3 h. The suspension was then left to stir open in a 60 ℃ oil bath until no visible liquid was observed, and then placed in a 60 ℃ oven to dry to obtain a white powder. Placing the white powder in a temperature programmed tube furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under the nitrogen atmosphere, keeping for 4h, and then cooling to room temperature to obtain light yellow three-dimensional porous carbon nitride powder (3D g-C)3N4）。
Example 1
A preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst comprises the step of taking 0.02g of vanadium-based ionic liquid [ (C)8H17)3NCH3]3H3V10O28Dissolving in 20mL of anhydrous ethanol, and collecting 0.08g of 3D g-C3N4Dispersing the powder in another 20mL of absolute ethyl alcohol, fully mixing the two by using a double-layer alloy disperser, stirring for 1 h at room temperature, completely transferring the mixed solution into a reaction kettle lined with a temperature-resistant and acid-resistant brick and lined with polytetrafluoroethylene, placing the reaction kettle into an air-blast drying oven to react for 24h at the temperature of 100 ℃, filtering and drying precipitates in the reaction kettle after cooling to room temperature, and obtaining the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst (20% -C)8V10O28/3D g-C3N4）。
From fig. 1, the infrared characteristic peaks of the vanadium-based ionic liquid and the three-dimensional porous carbon nitride can be clearly seen, which indicates that the supported catalyst is successfully prepared;
from fig. 2, the X-ray diffraction peak of the three-dimensional porous carbon nitride can be seen, and the characteristic peak of the vanadium-based ionic liquid can be detected after the loading amount is increased, which indicates that the target catalyst is prepared.
It can be seen from fig. 3 that the prepared carbon nitride has a three-dimensional porous structure, the pore structure is not damaged after the vanadium-based ionic liquid is loaded, and the ionic liquid is fully dispersed on the surface and in the pores of the three-dimensional porous carbon nitride.
Oxidation desulfurization performance of three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst
The three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst obtained in the example 1 is applied to the removal of dibenzothiophene sulfur-containing compounds in model oil by activated air catalytic oxidation, and the specific test conditions are as follows: taking 0.01 g of catalyst, controlling the reaction temperature to be 120 ℃, controlling the air flow rate to be 100 mL/min, controlling the consumption of model oil to be 20mL (wherein the initial content of DBT, 4-MDBT and 4,6-DMDBT is 200 ppm), sampling once every 1 h after the reaction starts, detecting by using a gas chromatograph to obtain the content of residual sulfur, and calculating the desulfurization rate.
From FIG. 4, it can be seen that the supported catalyst can remove all three dibenzothiophene sulfides to within 10 ppm after reacting for 6h under appropriate reaction conditions.
Example 2
A preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst comprises the step of adding vanadium-based ionic liquid [ (C)8H17)3NCH3]3H3V10O28(abbreviated as C)8V10O28) And 3D g-C3N4Respectively dispersing in absolute ethyl alcohol with the same volume, wherein the vanadium-based ionic liquid C8V10O28And 3D g-C3N4And absolute ethyl alcohol in a mass-to-volume ratio of 0.01 g to 0.09g to 20mL, fully stirring and mixing the two, transferring the mixture into a reaction kettle lined with a temperature-resistant and acid-resistant brick and lined with polytetrafluoroethylene to perform solvothermal reaction at 120 ℃ for 12 hours; the product obtained by separation is dried for 8 hours at the temperature of 80 ℃, and the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst (10% -C) can be obtained8V10O28/3D g-C3N4）。
The three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst obtained in the example 2 is applied to the removal of dibenzothiophene sulfur-containing compounds in model oil through activated air catalytic oxidation, and the residual sulfur content after 6 hours of reaction is 19.1 ppm.
Example 3
A preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst comprises the step of adding vanadium-based ionic liquid [ (C)8H17)3NCH3]3H3V10O28(abbreviated as C)8V10O28) And 3D g-C3N4Respectively dispersing in absolute ethyl alcohol with the same volume, wherein the vanadium-based ionic liquid C8V10O28And 3D g-C3N4And absolute ethyl alcohol in a mass-to-volume ratio of 0.03 g to 0.07 g to 15 mL, fully stirring and mixing the two, transferring the mixture into a reaction kettle lined with a temperature-resistant acid-resistant brick and lined with polytetrafluoroethylene to carry out solvothermal reaction at 100 ℃ for 36 hours; the product obtained by separation is dried for 3 hours at the temperature of 120 ℃, and the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst (30-C) can be obtained8V10O28/3D g-C3N4）。
The three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst obtained in example 3 is applied to removal of dibenzothiophene sulfur-containing compounds in model oil through activated air catalytic oxidation, and the residual sulfur content after 6 hours of reaction is 21.1 ppm.
Example 4
A preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst comprises the step of adding vanadium-based ionic liquid [ (C)4H9)3NCH3]3H3V10O28(abbreviated as C)4V10O28) And 3D g-C3N4Respectively dispersing in absolute ethyl alcohol with the same volume, wherein the vanadium-based ionic liquid C4V10O28And 3D g-C3N4And absolute ethyl alcohol in a mass-to-volume ratio of 0.02g to 0.08g to 20mL, fully stirring and mixing the two, transferring the mixture into a reaction kettle lined with a temperature-resistant acid-resistant brick and lined with polytetrafluoroethylene for solvothermal reaction at 100 ℃ for 24 hours; the product obtained by separation is dried for 6 hours at 100 ℃, and the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst (20-C) can be obtained4V10O28/3D g-C3N4）。
The three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst obtained in the example 4 is applied to the removal of dibenzothiophene sulfur-containing compounds in model oil through activated air catalytic oxidation, and the residual sulfur content after 6 hours of reaction is 25.2 ppm.
Blank control example
Taking the vanadium-based ionic liquid C in example 18V10O28Dispersed in absolute ethanol, C8V10O28The mass-volume ratio of the dispersion liquid to absolute ethyl alcohol is 0.02g: 20mL, and the dispersion liquid is transferred to a reaction kettle lined with temperature-resistant and acid-resistant bricks and lined with polytetrafluoroethylene for solvothermal reaction; another 3D g-C sample of example 1 was taken3N4Dispersed in absolute ethanol, 3D g-C3N4The mass-to-volume ratio of the dispersion to absolute ethyl alcohol is 0.08g:20mL, the dispersion is transferred to another reaction kettle which is lined with a temperature-resistant acid-resistant brick and lined with polytetrafluoroethylene for solvothermal reaction, the solvothermal reaction temperature of the two reaction kettles is 100 ℃, and the solvothermal reaction time is 24 hours; separating the obtained product, drying at 100 deg.C for 5 h to obtain blank control C8V10O28And 3D g-C3N4A catalyst.
Subjecting the obtained C to8V10O28And 3D g-C3N4The catalysts are respectively applied to the catalytic oxidation removal of dibenzothiophene sulfur-containing compounds in model oil by activating air, and the residual sulfur content after 6 hours of reaction is respectively 50.6 ppm and 182.2 ppm.
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 (8)
1. A preparation method of a three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst is characterized by comprising the following steps: mixing vanadium-based ionic liquid [ (C)nH2n+1)3NCH3]3H3V10O28The cationic carbon chain length n is 2,4,8, abbreviated as CnV10O28And 3Dg-C3N4Respectively dispersing in absolute ethyl alcohol with the same volume, wherein the vanadium-based ionic liquid CnV10O28And 3D g-C3N4And absolute ethyl alcohol in a mass-to-volume ratio of 0.01-0.04 g to 0.06-0.09 g to 15-20 mL, fully stirring and mixing the two, transferring the mixture into a reaction kettle lined with a temperature-resistant and acid-resistant brick inside and lined with polytetrafluoroethylene to perform solvothermal reaction for 12-36 h at 100-150 ℃, and separating the obtained product to dry for 1-8 h at 80-120 ℃ to obtain the catalyst.
2. The preparation method of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst according to claim 1, characterized in that: the vanadium-based ionic liquid CnV10O28And 3D g-C3N4And the mass-to-volume ratio of the absolute ethyl alcohol is 0.02g to 0.08g to 20 mL.
3. The preparation method of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst according to claim 1, characterized in that: the time for fully stirring the mixture is 0.5-2 h.
4. The preparation method of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst according to claim 1, characterized in that: the solvothermal reaction temperature is 100 ℃, and the time is 24 hours.
5. The preparation method of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst according to claim 1, characterized in that: the drying temperature of the product is 100 ℃ and the time is 6 h.
6. The three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst prepared by the method of any one of claims 1 to 5.
7. The application of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst as claimed in claim 6, wherein: the catalyst is applied to the field of catalytic oxidation desulfurization.
8. The application of the three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst according to claim 7, is characterized in that: the method is applied to the efficient oxidation removal of dibenzothiophene sulfides in fuel oil by taking air as an oxidant.
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