CN111841629A - Preparation method and desulfurization application of few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst - Google Patents
Preparation method and desulfurization application of few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 68
- 125000005496 phosphonium group Chemical group 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
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- 239000012467 final product Substances 0.000 claims description 3
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- MVVMXXNXJFRKON-UHFFFAOYSA-N 4,6-dimethyl-5-sulfanylidenedibenzothiophene Chemical class C12=CC=CC(C)=C2S(=S)C2=C1C=CC=C2C MVVMXXNXJFRKON-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000005342 ion exchange Methods 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
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- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
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- 239000011593 sulfur Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000193 wide-angle powder X-ray diffraction Methods 0.000 description 1
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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
- B01J31/02—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
- B01J31/0292—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 immobilised on a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
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Abstract
The invention discloses a preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst and a desulfurization application thereof, wherein the preparation method comprises the following steps: preparation of quaternary phosphonium type heteropoly acid ionic liquid [ C ] by ion exchange method14H29P(C6H13)3]3PM12O40And preparing few-layer graphite-like phase carbon nitride by a thermal polycondensation method, and preparing the supported ionic liquid catalysts with different loading amounts by a solvothermal method. The invention also discloses application of the supported ionic liquid catalyst prepared by the method in the field of catalytic oxidation desulfurization. The invention utilizes cheap and easily-obtained nitrogen-containing precursor raw materials to prepare the large-surface-area few-layer graphite-like carbon nitride through thermal polycondensation, and the carbon nitride is used as a carrier to load different quaternary phosphonium ionsAnd the sub-liquid is used for screening out a supported ionic liquid catalyst with high-efficiency catalytic oxidation desulfurization performance by regulating the anion type and the loading capacity of the ionic liquid, deeply removing sulfides such as dibenzothiophene and 4, 6-dimethyl dibenzothiophene in fuel oil, and achieving the deep desulfurization target.
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 few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst.
Technical Field
Sulfur Oxides (SO) produced after combustion of sulfur-containing compounds in fuel oil x ) Causing serious environmental pollution. On the one hand SO x Direct discharge into the atmosphere can lead to air pollution; on the other hand, SO x The discharge of (a) can form acid rain, cause corrosion to trees, buildings, and also lead to soil acidification. At the same time, SO x And the catalyst of the tail gas treatment device of the automobile engine is poisoned, so that the discharge amount of nitrogen oxides and particulate matters in the tail gas of the automobile is increased, and the environmental pollution is further aggravated. Therefore, the desulfurization treatment of the fuel and the production of clean fuel are effective ways for controlling the pollution from the source. Currently, most countries and regions around the world require that the sulfur content in vehicle fuel oil is lower than 10 ppm, the existing hydrodesulfurization technology needs expensive cost and equipment investment to remove Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) sulfides, and the oxidative desulfurization technology capable of efficiently removing the Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) sulfides under mild conditions gets more and more attention.
The introduction of a proper catalyst into the oxidation desulfurization technology (ODS) can greatly improve the catalytic oxidation desulfurization efficiency. Researches show that the functionalized ionic liquid has good catalytic oxidation desulfurization performance, but the popularization of the ionic liquid in the field of catalytic oxidation desulfurization is hindered due to the reasons that the dosage of the ionic liquid in the reaction is large, the liquid-liquid separation after the reaction is difficult and the like, if the ionic liquid is selectedThe problem of large amount can be effectively solved by constructing the supported ionic liquid catalyst by using a proper carrier. In recent years, graphite-like phase carbon nitride (g-C) having a large surface area3N4) The material is selected as a carrier and widely applied to a plurality of fields of catalysis, water photolysis hydrogen production, environmental pollutant degradation and the like, g-C3N4Is a potential carrier material for constructing a supported ionic liquid catalyst.
The invention selects cheap and easily-obtained nitrogen source precursor, and prepares the few-layer g-C by thermal polycondensation3N4And as a carrier; preparing quaternary phosphonium type heteropoly acid ionic liquid by an ion exchange method and loading the quaternary phosphonium type heteropoly acid ionic liquid to g-C3N4Thus, a series of supported ionic liquid catalysts with different types and different loading amounts are obtained. The catalyst can efficiently catalyze, oxidize and remove DBT and 4,6-DMDBT sulfur-containing compounds in fuel oil under mild conditions, can be used as a supplementary technology of a hydrodesulfurization technology, and has good application prospect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst to obtain a supported catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst comprises the following steps: reacting a quaternary phosphonium type ionic liquid [ C14H29P(C6H13)3]3PM12O40(abbreviated as C)14PPM) and few layers g-C3N4Respectively dispersing the two into dichloromethane, fully stirring and mixing the two, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, cooling to room temperature, volatilizing the solvent, and drying in an air-blast drying oven to obtain the final product.
Preferably, in the preparation method of the quaternary phosphonium ionic liquid catalyst supported by the few-layer graphite-like carbon nitride: the quaternary phosphonium ionic liquid C14In PPM, M =W or Mo.
Preferably, in the preparation method of the quaternary phosphonium ionic liquid catalyst supported by the few-layer graphite-like carbon nitride: the quaternary phosphonium ionic liquid C14PPM and minor layer g-C3N4The solid-liquid ratio of the quaternary phosphonium ionic liquid to dichloromethane is 0.01-0.06 g: 0.14-0.19 g: 10-30 mL, and the load capacity of the quaternary phosphonium ionic liquid is 5-30%.
Preferably, in the preparation method of the quaternary phosphonium ionic liquid catalyst supported by the few-layer graphite-like carbon nitride: c14PPM and minor layer g-C3N4The time for dispersing and stirring in dichloromethane is 0.5-3 h.
Preferably, in the preparation method of the quaternary phosphonium ionic liquid catalyst supported by the few-layer graphite-like carbon nitride: the solvothermal reaction temperature is 100-140 ℃, and the solvothermal reaction time is 8-24 hours.
Preferably, in the preparation method of the quaternary phosphonium ionic liquid catalyst supported by the few-layer graphite-like carbon nitride: the drying temperature of the product is 80-120 ℃, and the drying time is 4-12 h.
The obtained few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst is applied to catalytic oxidation desulfurization. The method is particularly applied to oxidizing and removing dibenzothiophene and 4, 6-dimethyl dibenzothiophene sulfides in fuel oil by using hydrogen peroxide as an oxidizing agent.
The functionalized ionic liquid shows excellent catalytic performance in the field of fuel oil oxidation desulfurization, but the ionic liquid is usually used in a large amount, so that the cost is high; meanwhile, the ionic liquid and the oil phase are difficult to separate liquid from liquid after reaction. The invention prepares the few-layer g-C with large specific surface area by utilizing the cheap and easily obtained nitrogen source for thermal polycondensation 3N4The ionic liquid is used as a carrier, the ionic liquid is highly dispersed, the dosage of the ionic liquid is greatly reduced, and the heterogeneous catalyst is easy to separate from an oil phase after reaction. The synthesized load type quaternary phosphonium ionic liquid has excellent catalytic oxidation removal performance on DBT and 4,6-DMDBT, and can be used as a supplementary technology of hydrodesulfurization to efficiently remove various sulfur-containing compounds in fuel oil and prepare clean oil products.
The synthesized supported catalyst is subjected to composition and morphological structure analysis by infrared spectroscopy (FT-IR), wide-angle X-ray powder diffraction (XRD), scanning electron microscope (SWM), Transmission Electron Microscope (TEM) and the like. DBT and 4,6-DMDBT are taken as typical sulfur-containing compounds to prepare model oil, and hydrogen peroxide is taken as an oxidant to apply the synthesized supported quaternary phosphonium ionic liquid catalyst 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).
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes cheap and easily available nitrogen source precursors to prepare few-layer graphite-like carbon nitride with large specific surface area, designs and synthesizes a series of quaternary phosphonium ionic liquid, combines the quaternary phosphonium ionic liquid and the quaternary phosphonium ionic liquid by a solvothermal method to obtain a supported ionic liquid catalyst, uses hydrogen peroxide as an oxidant, and efficiently removes DBT and 4, 6-DMDBT-like sulfur-containing compounds which are difficult to remove in the hydrodesulfurization technology.
Drawings
FIG. 1 is a FT-IR spectrum of the catalyst;
(a) C14PPMo, (b) g-C3N4, (c) 5% C14PPMo/g-C3N4,and (d) 30% C14PPMo/g-C3N4
FIG. 2 is a wide angle XRD spectrum of the catalyst;
(a) C14PPMo, (b) g-C3N4, (c) 5% C14PPMo/g-C3N4,and (d) 30% C14PPMo/g-C3N4
FIG. 3 is SEM and TEM photographs of the catalyst;
(A) and (B):SEM images; (C) and (D): TEM images
(A) and (C): g-C3N4; (B) and (D) 5% C14PPMo/g-C3N4
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.
Example 1:
a preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst comprises the following steps: taking 0.19 g of small layer g-C3N4The powder is dispersed in 10 mLCH2Cl2And (5) carrying out ultrasonic treatment for 1 h to obtain a mixed solution A. 0.01 g of quaternary phosphonium type ionic liquid [ C ] was taken14H29P(C6H13)3]3PMo12O40(abbreviated as C)14PPMo), 6 mL of CH was added2Cl2And stirring and dissolving uniformly to obtain a solution B. Adding the solution B into the mixed solution A dropwise under the condition of 50 ℃ water bath, and using 4 mL of CH2Cl2Washed and stirred continuously for 3 h. Then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, standing for 24 h at 100 ℃, cooling to room temperature, volatilizing the solvent, drying the obtained solid at 80 ℃ for 12 h to obtain the few-layer graphite-like carbon nitride-loaded quaternary phosphonium ionic liquid catalyst (5% C)14PPMo/g-C3N4）。
Example 2:
A preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst comprises the following steps: taking 0.14 g of small layer g-C3N4The powder is dispersed in 10 mLCH2Cl2And (5) carrying out ultrasonic treatment for 1 h to obtain a mixed solution A. 0.06 g of quaternary phosphonium type ionic liquid [ C ] was taken14H29P(C6H13)3]3PMo12O40(abbreviated as C)14PPMo), 6 mL of CH was added2Cl2And stirring and dissolving uniformly to obtain a solution B. Adding the solution B into the mixed solution A dropwise under the condition of 50 ℃ water bath, and using 4 mL of CH2Cl2Washed and stirred continuously for 2 h. Then mixing the mixed solutionTransferring into a reaction kettle with polytetrafluoroethylene lining, standing at 120 deg.C for 16 h, cooling to room temperature, volatilizing solvent, oven drying the obtained solid at 100 deg.C for 8 h to obtain the final product14PPMo/g-C3N4）。
From FIG. 1, the infrared characteristic peaks of the quaternary phosphonium type phosphomolybdic ion liquid and the few-layer graphite-like 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 few-layer graphite-like carbon nitride can be seen, and the characteristic peak of the quaternary phosphonium type phosphomolybdic ion liquid can be detected after the loading capacity is increased, which indicates that the target catalyst is prepared.
From fig. 3, it can be seen that the prepared carbon nitride has a lamellar structure, the lamellar structure is not damaged after the quaternary phosphonium type phosphorus molybdenum ionic liquid is loaded, and the ionic liquid is highly dispersed on the surface of the lamellar graphite-like carbon nitride.
Example 3:
a preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst comprises the following steps: taking 0.18 g of small layer g-C3N4The powder is dispersed in 10 mLCH2Cl2And (5) carrying out ultrasonic treatment for 1 h to obtain a mixed solution A. 0.02 g of quaternary phosphonium type ionic liquid [ C ] was taken14H29P(C6H13)3]3PW12O40(abbreviated as C)14PPW), 6 mL of CH was added2Cl2And stirring and dissolving uniformly to obtain a solution B. Adding the solution B into the mixed solution A dropwise under the condition of 50 ℃ water bath, and using 4 mL of CH2Cl2Washed and stirred continuously for 1 h. Then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, standing for 8 hours at 140 ℃, cooling to room temperature, volatilizing the solvent, drying the obtained solid for 4 hours at 120 ℃, and obtaining the few-layer graphite-like carbon nitride-loaded quaternary phosphonium ionic liquid catalyst (10% C)14PPW/g-C3N4）。
Example 4:
oxidation desulfurization performance of few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst
The few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst obtained in the example 1 is applied to catalytic oxidation removal of DBT and 4,6-DMDBT in model oil, and the specific test conditions are as follows: 0.05 g of catalyst is taken, the reaction temperature is 60 ℃, n (O)/n (S) is 4, the dosage of model oil is 5 mL (wherein the initial content of DBT and 4,6-DMDBT is 500 ppm and 250ppm respectively), sampling is carried out every 20 min after the reaction is started, and gas chromatography is used for detection, so that the residual sulfur content is obtained and the desulfurization rate is calculated.
As can be seen from FIG. 4, after the supported catalyst reacts for 180 min under the set conditions, the removal rate of DBT reaches 100%, the removal rate of 4,6-DMDBT is 94.8%, and the residual sulfur content is 13 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 (9)
1. A preparation method of a few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst is characterized by comprising the following steps of: mixing quaternary phosphonium ionic liquid C14PPM and few layers g-C3N4Respectively dispersing the two into dichloromethane, fully stirring and mixing the two, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining for solvent heat treatment, cooling to room temperature, volatilizing the solvent, and drying in an air-blast drying oven to obtain the final product.
2. The method for preparing the few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: the quaternary phosphonium ionic liquid C14In PPM, M = W or Mo.
3. The method for preparing the few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: the quaternary phosphonium ionic liquid C 14PPM and minor layer g-C3N4The solid-liquid ratio of the quaternary phosphonium ionic liquid to dichloromethane is 0.01-0.06 g: 0.14-0.19 g: 10-30 mL, and the load capacity of the quaternary phosphonium ionic liquid is 5-30%.
4. The method for preparing the few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: c14PPM and minor layer g-C3N4The time for dispersing and stirring in dichloromethane is 0.5-3 h.
5. The method for preparing the few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: the solvothermal reaction temperature is 100-140 ℃, and the solvothermal reaction time is 8-24 hours.
6. The method for preparing the few-layer graphite-like carbon nitride supported quaternary phosphonium ionic liquid catalyst according to claim 1, wherein the method comprises the following steps: the drying temperature of the product is 80-120 ℃, and the drying time is 4-12 h.
7. The quaternary phosphonium ionic liquid catalyst supported by the graphite-like carbon nitride with few layers prepared by the method of any one of claims 1 to 6.
8. The use of the quaternary phosphonium ionic liquid catalyst supported on the few-layer graphite-like carbon nitride according to claim 7 in catalytic oxidative desulfurization.
9. Use according to claim 8, characterized in that: the method is applied to oxidizing and removing dibenzothiophene and 4, 6-dimethyl dibenzothiophene sulfides in fuel oil by using hydrogen peroxide as an oxidizing agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112642479A (en) * | 2020-12-23 | 2021-04-13 | 江苏大学 | Preparation method and desulfurization application of few-layer carbon nitride supported molybdenum-based ionic liquid catalyst |
| CN113893878A (en) * | 2021-10-15 | 2022-01-07 | 海南师范大学 | Preparation method and application of nanofiber-supported heteropolyacid salt catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214878A (en) * | 2013-04-02 | 2013-07-24 | 江苏大学 | Preparation method of graphite type carbon nitride-ionic liquid composite material |
| CN103736521A (en) * | 2014-01-28 | 2014-04-23 | 江苏大学 | Preparation method of graphene-like boron nitride loading ionic liquid catalyst and application thereof |
| CN103992814A (en) * | 2014-05-29 | 2014-08-20 | 江苏大学 | Method for desulfurization of fuel oil in catalytic oxidation manner via ionic liquid |
| CN110124711A (en) * | 2019-04-04 | 2019-08-16 | 江苏大学 | The preparation method and its desulfurization application of few layer carbonitride loaded tungsten trioxide nanoparticle catalyst |
| CN110833867A (en) * | 2019-10-25 | 2020-02-25 | 江苏大学 | Preparation method and desulfurization application of three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst |
-
2020
- 2020-06-22 CN CN202010571421.5A patent/CN111841629A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214878A (en) * | 2013-04-02 | 2013-07-24 | 江苏大学 | Preparation method of graphite type carbon nitride-ionic liquid composite material |
| CN103736521A (en) * | 2014-01-28 | 2014-04-23 | 江苏大学 | Preparation method of graphene-like boron nitride loading ionic liquid catalyst and application thereof |
| CN103992814A (en) * | 2014-05-29 | 2014-08-20 | 江苏大学 | Method for desulfurization of fuel oil in catalytic oxidation manner via ionic liquid |
| CN110124711A (en) * | 2019-04-04 | 2019-08-16 | 江苏大学 | The preparation method and its desulfurization application of few layer carbonitride loaded tungsten trioxide nanoparticle catalyst |
| CN110833867A (en) * | 2019-10-25 | 2020-02-25 | 江苏大学 | Preparation method and desulfurization application of three-dimensional porous carbon nitride supported vanadium-based ionic liquid catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李旭贺等: "石墨相氮化碳负载磷钨酸杂化材料的制备及其氧化脱硫催化性能", 《燃料化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112642479A (en) * | 2020-12-23 | 2021-04-13 | 江苏大学 | Preparation method and desulfurization application of few-layer carbon nitride supported molybdenum-based ionic liquid catalyst |
| CN113893878A (en) * | 2021-10-15 | 2022-01-07 | 海南师范大学 | Preparation method and application of nanofiber-supported heteropolyacid salt catalyst |
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