CN112642479A - Preparation method and desulfurization application of few-layer carbon nitride supported molybdenum-based ionic liquid catalyst - Google Patents
Preparation method and desulfurization application of few-layer carbon nitride supported molybdenum-based ionic liquid catalyst Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 64
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 46
- 239000011733 molybdenum Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 27
- 230000023556 desulfurization Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000295 fuel oil Substances 0.000 claims abstract description 11
- 229910020881 PMo12O40 Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 2
- 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 1
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 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 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
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- 239000012071 phase Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 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 description 2
- NFKMSYOEMWGTMW-UHFFFAOYSA-N 5-sulfanylidenedibenzothiophene Chemical class C1=CC=C2S(=S)C3=CC=CC=C3C2=C1 NFKMSYOEMWGTMW-UHFFFAOYSA-N 0.000 description 2
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- B01J31/0294—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 by polar or ionic interaction with the substrate, e.g. glass
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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
- 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
- B01J27/19—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
- B01J27/24—Nitrogen compounds
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- 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
- B01J31/0281—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 nitrogen being a ring member
- B01J31/0284—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 nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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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- 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 material preparation and catalytic reaction, relates to catalytic oxidation desulfurization, and particularly relates to a preparation method of a few-layer carbon nitride supported molybdenum-based ionic liquid catalyst, which comprises the following steps: respectively taking molybdenum-based ionic liquid [ Cnmim]3PMo12O40And few layers g-C3N4Dispersing in dichloromethane, mixing the two dispersions, stirring, and transferring the mixture to the liningCarrying out solvothermal reaction for 8-36 h at the temperature of 100-160 ℃ in a reaction kettle of the fluoroethylene, cooling to room temperature, volatilizing the solvent and drying. The preparation method is simple and easy to popularize, and has few g-C layers3N4Has larger specific surface area and is an ideal catalyst carrier. The invention uses hydrogen peroxide as an oxidant to construct a heterogeneous catalytic oxidation desulfurization system, efficiently removes sulfur-containing compounds in fuel oil, and the supported ionic liquid catalyst can be repeatedly utilized, thereby solving the problems of large ionic liquid consumption in homogeneous reaction, difficult separation and recovery after reaction and the like.
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 carbon nitride supported molybdenum-based ionic liquid catalyst.
Background
At present, strict legal regulations are established on sulfur content of vehicle fuel oil (gasoline and diesel oil) worldwide, and the sulfur content in the fuel oil is required to be not more than 10 ppm. The combustion product of the sulfide in the fuel oil is sulfur oxide, which is one of the sources for forming acid rain and has corrosive effect on the atmosphere, soil, forest, buildings and the like; meanwhile, the sulfur oxides can also influence the normal operation of a vehicle exhaust treatment device, aggravate the emission of particulate matters and nitrogen oxides in the exhaust, influence the air quality and harm the human health. The gasoline and diesel oil desulfurization method widely used in China is a hydrodesulfurization method, and can meet the requirements of industrial production and environmental protection regulations. However, the hydrodesulfurization method needs to remove Dibenzothiophene (DBT) sulfides efficiently under conditions of high temperature, high pressure and the like, which leads to a great increase in the cost of producing clean fuel oil. Therefore, the development of a method for efficiently removing dibenzothiophene sulfides in fuel under mild conditions is an important research topic in the petrochemical industry.
The oxidative desulfurization technology is considered to be one of high-efficiency desulfurization methods with great application prospects, the method has mild operation conditions and excellent desulfurization performance on various dibenzothiophene sulfides. And a proper catalyst is added in the oxidation desulfurization process, so that the catalytic oxidation desulfurization efficiency can be greatly improved. The ionic liquid is considered as a designable solvent, has stable physicochemical properties, can obtain the functionalized ionic liquid with excellent catalytic performance by regulating and controlling the species of anions and cations of the ionic liquid, and shows unique advantages in the field of early oxidative desulfurization. However, the ionic liquid phase and the oil phase have the problem that they are difficult to completely separate after the reaction, and the amount of the ionic liquid used is generally large. Therefore, the problems in two aspects can be solved by introducing a proper carrier to construct a supported ionic liquid catalyst and constructing a heterogeneous catalytic oxidation desulfurization system.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a preparation method of a few-layer carbon nitride supported molybdenum-based ionic liquid catalyst, and the supported catalyst is obtained.
The invention adopts a low-cost and easy-to-operate method to prepare the few-layer carbon nitride (g-C) with larger specific surface area3N4) The material is used as a carrier for loading imidazole type molybdenum-based ionic liquid with the oxidative desulfurization performance of activated hydrogen peroxide, so as to construct a series of supported ionic liquid catalysts with different types and loading capacity. The catalyst can remove various sulfides such as DBT, 4-methyl dibenzothiophene (4-MDBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) and the like in fuel oil by oxidation under mild conditions by using hydrogen peroxide as an oxidant, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
carbon nitride (g-C) with few layers3N4) The preparation method of the supported molybdenum-based ionic liquid catalyst comprises the following steps: respectively taking molybdenum-based ionic liquid [ Cnmim]3PMo12O40(abbreviated as C)nPMo) and few layers g-C3N4Dispersing in dichloromethane, mixing the two dispersion solutions, fully and uniformly stirring, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction for 8-36 h at 100-160 ℃, cooling to room temperature, volatilizing the solvent and drying to obtain the polytetrafluoroethylene composite material.
In the preferred embodiment of the invention, the molybdenum-based ionic liquidCnIn PMo, n = 4, 8, 12 or 16.
In the preferred embodiment of the invention, the molybdenum-based ionic liquid CnPMo and few layers g-C3N4The solid-liquid ratio of the molybdenum ion liquid to dichloromethane is 0.002-0.1 g, 0.1-0.198 g and 10-25 mL, and the load capacity of the molybdenum ion liquid is 1-50%.
In a preferred embodiment of the present invention, CnPMo and few layers g-C3N4The stirring and dispersing time in dichloromethane is 1-5 h.
In the preferred embodiment of the invention, the mixed solution is transferred to a reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction at 130 ℃ for 22 hours.
In the preferred disclosed embodiment of the invention, the solvent is volatilized and dried after being cooled to room temperature, and the drying temperature is 60-120 ℃ and the drying time is 6-24 hours.
The molybdenum-based ionic liquid [ C ] of the inventionnmim]3PMo12O40The preparation method comprises the following steps:
take 3 mmol of [ C ]nmim]Cl (where n = 4, 8, 12, or 16) in a 250 mL beaker, 100 mL deionized water was added and magnetically stirred until well dispersed; another 1 mmol H3PMo12O40·nH2O into a 50 mL beaker, 25 mL of deionized water was added, stirred to dissolve it, and slowly added dropwise to [ C ]nmim]In an aqueous solution of Cl, the beaker was washed 3 times with 25 mL of deionized water, and the washing solution was added slowly to [ C ]nmim]Continuing to magnetically stir for 3 hours in the Cl aqueous solution; standing the mixed solution, performing suction filtration, washing with a large amount of deionized water, and drying a filter cake in a vacuum drying oven at 50 ℃ to obtain the product [ Cnmim]3PMo12O40(abbreviated as C)nPMo, n = 4, 8, 12 or 16), the resulting solid was ground to a fine powder with a mortar.
The few-layer carbon nitride (g-C) of the present invention3N4) The preparation method comprises the following steps:
weighing 10 g of melamine in a temperature programming muffle furnace, raising the temperature to 550 ℃ at a temperature rise rate of 2 ℃/min in an air atmosphere, keeping the temperature for 4 h to obtain yellow solid, and grinding the yellow solidGrinding into powder; then weighing 3 g of yellow powder, continuously increasing the temperature to 500 ℃ at the temperature rising rate of 5 ℃ per min in the air atmosphere, and keeping the temperature for 2 h to obtain a final product, namely a pale yellow solid with few layers of g-C3N4。
The invention also aims to apply the prepared few-layer carbon nitride supported molybdenum-based ionic liquid catalyst to catalytic oxidation desulfurization.
Specifically, the method is applied to oxidizing and removing sulfides such as dibenzothiophene, 4-methyl dibenzothiophene and 4, 6-dimethyl dibenzothiophene in fuel oil by using 30 wt.% of hydrogen peroxide as an oxidant.
The imidazole type molybdenum-based ionic liquid shows excellent catalytic performance in a homogeneous fuel oil oxidation desulfurization system, but has the problems of difficulty in complete separation from an oil phase after reaction, large dosage of the ionic liquid and the like, and further popularization and application of the imidazole type molybdenum-based ionic liquid are limited. According to the invention, the supported ionic liquid is prepared, a heterogeneous catalytic oxidation desulfurization system is constructed, the dispersion of active ingredients and the contact with a substrate are promoted by the large specific surface area of the carrier, the dosage of the ionic liquid in the reaction is reduced, and the heterogeneous catalyst is easy to separate and recycle after the reaction and can be repeatedly used. The constructed supported molybdenum-based ionic liquid has good activated hydrogen peroxide desulfurization performance, has high-efficiency catalytic oxidation removal capacity on various sulfides such as DBT, 4-MDBT, 4,6-DMDBT and the like in fuel oil, and can be combined with a hydrodesulfurization technology in practical application to produce clean oil products under mild conditions.
By infrared spectroscopic analysis (FT-IR), N2Adsorption-desorption isotherm and Transmission Electron Microscope (TEM) and other characterization methods for the prepared molybdenum-based ionic liquid and few layers of g-C3N4And carrying out composition and morphological structure analysis on the supported ionic liquid catalyst. DBT, 4-MDBT and 4,6-DMDBT are taken as typical sulfur-containing compounds to prepare model oil, 30 wt.% of hydrogen peroxide is taken as an oxidant, and the prepared supported molybdenum-based ionic liquid catalyst is applied to catalytic oxidation desulfurization reaction. And detecting the residual quantity of sulfide in the model oil after reaction by a gas chromatograph to investigate the catalytic oxidation desulfurization performance of the supported catalyst.
Advantageous effects
The invention prepares the g-C with few layers by using a low-cost and easy-to-operate method3N4The material has larger specific surface area and is an ideal catalyst carrier; synthesizing imidazole type molybdenum-based ionic liquids with different carbon chain lengths by an ion exchange method; and the supported molybdenum-based ionic liquid catalyst is obtained by combining the two by utilizing a solvothermal method, and the preparation method is simple and easy to popularize. Meanwhile, a heterogeneous catalytic oxidation desulfurization system is constructed by taking hydrogen peroxide as an oxidant, sulfur-containing compounds such as DBT, 4-MDBT, 4,6-DMDBT and the like in the fuel oil are efficiently removed, and the supported ionic liquid catalyst can be repeatedly utilized for multiple times, so that the problems of large ionic liquid consumption, difficulty in separation and recovery after reaction and the like in a homogeneous reaction are solved.
Drawings
FIG. 1 FT-IR spectra of different samples, in which (a) 1% -C12PMo/g-C3N4, (b) 3%-C12PMo/g-C3N4, (c) 5%-C12PMo/g-C3N4, (d) 10%-C12PMo/g-C3N4, (e) 50%-C12PMo/g-C3N4, (f) g-C3N4, (g) C12PMo；
FIG. 2. N of different samples2Adsorption-desorption curve chart;
FIG. 3 TEM photograph of few-layer carbon nitride and supported ionic liquid catalyst, in which (A) C3N4, (B) 5%-C12PMo/g-C3N4；
FIG. 4 is a graph of catalytic oxidative removal performance for different sulfur-containing substrates;
FIG. 5 shows the desulfurization rate of DBT after reacting for 90 min with different catalyst loadings.
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 carbon nitride supported molybdenum-based ionic liquid catalyst comprises the following steps: taking 0.198 g of small layer g-C3N4The powder is dispersed in 12 mLCH2Cl2And (5) carrying out ultrasonic treatment for 1 h to obtain a mixed solution A. 0.002 g of molybdenum-based ionic liquid [ C ] is taken12mim]3PMo12O40(abbreviated as C)12PMo), 8 mL 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 5 mL of CH2Cl2Washed and stirred continuously for 2.5 h. Then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, standing at 120 ℃ for 24 h, cooling to room temperature, volatilizing the solvent, drying the obtained solid at 100 ℃ for 12 h to obtain the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst (1% -C)12PMo/g-C3N4）。
Example 2
A preparation method of a few-layer carbon nitride supported molybdenum-based 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. 0.02 g of quaternary phosphonium type ionic liquid [ C ] was taken12mim]3PMo12O40(abbreviated as C)12PMo), 10 mL 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 5 mL of CH2Cl2Washed and stirred continuously for 3 h. Then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, standing at 140 ℃ for 12 h, cooling to room temperature, volatilizing the solvent, drying the obtained solid at 80 ℃ for 16 h to obtain the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst (5% -C)12PMo/g-C3N4）。
Example 3
A preparation method of a few-layer carbon nitride supported molybdenum-based ionic liquid catalyst comprises the following steps: taking 0.1 g of small layer g-C3N4The powder is dispersed in 15 mLCH2Cl2And (5) carrying out ultrasonic treatment for 1 h to obtain a mixed solution A. Then 0.1 g of molybdenum-based ionic liquid [ C ] is taken12mim]3PMo12O40(abbreviated as C)12PMo), 15 are added mL CH2Cl2And 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 5 mL of CH2Cl2Washed and stirred continuously for 4 h. Then transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, standing for 36 h at 100 ℃, cooling to room temperature, volatilizing the solvent, drying the obtained solid for 8 h at 120 ℃, and obtaining the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst (50% -C)12PMo/g-C3N4）。
From fig. 1, it is evident that the supported ionic liquid has infrared characteristic peaks of few layers of carbon nitride and molybdenum-based ionic liquids at the same time, indicating the successful preparation of the supported ionic liquid catalyst;
from fig. 2, it can be seen that the catalysts with different ionic liquid loading have a certain pore structure, and the specific surface area is gradually reduced along with the increase of the loading;
as can be seen from fig. 3, before and after loading the ionic liquid, the carrier carbon nitride is a layered structure, and when the loading amount is 5%, the ionic liquid is uniformly dispersed on the surface of the few layers of carbon nitride.
Catalytic oxidation desulfurization application of few-layer carbon nitride supported molybdenum-based ionic liquid catalyst
The few-layer carbon nitride supported molybdenum-based ionic liquid catalyst (5% -C) obtained in example 212PMo/g-C3N4) The method is applied to catalytic oxidation removal of DBT, 4-MDBT and 4,6-DMDBT in model oil (wherein the initial content of DBT, 4-MDBT and 4,6-DMDBT is 500 ppm, 500 ppm and 250 ppm respectively), and the specific reaction conditions are as follows: m (catalyst) = 0.05 g, reaction temperature T = 60 ℃, n (o)/n(s) = 2, V (model oil) = 5 mL. Sampling the upper oil phase once every 10 min after the reaction starts, detecting by using a gas chromatograph, and calculating the desulfurization rate according to the residual sulfur content.
It can be seen from fig. 4 that after the supported ionic liquid catalyst reacts for 90 min under the given conditions, the removal rate of DBT reaches 95.1%, and the removal rates of 4-MDBT and 4,6-DMDBT are 91.8% and 80.6%, respectively, at this time, the amount of the oxidant hydrogen peroxide is the stoichiometric amount, and sulfide in the model oil can be completely removed by properly increasing the amount of hydrogen peroxide.
In addition, the DBT removal rates of the catalysts obtained in example 1 and example 3 after 90 min of reaction under the same conditions as in example 2 were 87.5% and 72.8%, respectively.
Fig. 5 shows the DBT desulfurization rates for catalysts with loadings of 1%, 3%, 5%, 10% and 50% after 90 min of reaction: 87.5%, 90.1%, 95.1%, 89% and 72.8%.
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 carbon nitride supported molybdenum-based ionic liquid catalyst is characterized by comprising the following steps: respectively taking molybdenum-based ionic liquid [ Cnmim]3PMo12O40(abbreviated as C)nPMo) and few layers g-C3N4Dispersing in dichloromethane, mixing the two dispersion solutions, fully and uniformly stirring, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out solvothermal reaction for 8-36 h at 100-160 ℃, cooling to room temperature, volatilizing the solvent and drying to obtain the polytetrafluoroethylene composite material.
2. The preparation method of the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst as claimed in claim 1, wherein the method comprises the following steps: the molybdenum-based ionic liquid CnIn PMo, n = 4, 8, 12 or 16.
3. The preparation method of the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst as claimed in claim 1, wherein the method comprises the following steps: the molybdenum-based ionic liquid CnPMo and few layers g-C3N4The solid-liquid ratio of the molybdenum ion liquid to dichloromethane is 0.002-0.1 g, 0.1-0.198 g and 10-25 mL, and the load capacity of the molybdenum ion liquid is 1-50%.
4. The few layer nitridation of claim 1The preparation method of the carbon-supported molybdenum-based ionic liquid catalyst is characterized by comprising the following steps: cnPMo and few layers g-C3N4The time for dispersing and stirring in dichloromethane is 1-5 h.
5. The preparation method of the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst as claimed in claim 1, wherein the method comprises the following steps: and transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction at 130 ℃ for 22 hours.
6. The preparation method of the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst as claimed in claim 1, wherein the method comprises the following steps: and volatilizing and drying the solvent after cooling to room temperature, wherein the drying temperature is 60-120 ℃, and the drying time is 6-24 h.
7. The few-layer carbon nitride supported molybdenum-based ionic liquid catalyst prepared by the method of any one of claims 1 to 6.
8. Use of the few-layer carbon nitride supported molybdenum-based ionic liquid catalyst of claim 7 in catalytic oxidative desulfurization.
9. Use according to claim 8, characterized in that: the method is applied to oxidizing and removing dibenzothiophene, 4-methyl dibenzothiophene and 4, 6-dimethyl dibenzothiophene sulfides in fuel oil by using hydrogen peroxide as an oxidant.
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| CN111841629A (en) * | 2020-06-22 | 2020-10-30 | 江苏中江材料技术研究院有限公司 | Preparation method and desulfurization application of few-layer graphite-phase carbon nitride supported quaternary phosphonium ionic liquid catalyst |
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