CN110560163A - preparation method of oleophylic magnetic carbon material loaded molybdenum oxide catalyst and application of catalyst in fuel oil desulfurization - Google Patents
preparation method of oleophylic magnetic carbon material loaded molybdenum oxide catalyst and application of catalyst in fuel oil desulfurization Download PDFInfo
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- CN110560163A CN110560163A CN201910802164.9A CN201910802164A CN110560163A CN 110560163 A CN110560163 A CN 110560163A CN 201910802164 A CN201910802164 A CN 201910802164A CN 110560163 A CN110560163 A CN 110560163A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 22
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 21
- 230000023556 desulfurization Effects 0.000 title claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 18
- 239000000295 fuel oil Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical group 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 8
- 229910052799 carbon Inorganic materials 0.000 claims 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 34
- 239000000047 product Substances 0.000 description 10
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 7
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 6
- 229910015711 MoOx Inorganic materials 0.000 description 6
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 5
- 238000010813 internal standard method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000446 fuel Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
Classifications
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- 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
-
- 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
- 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
-
- 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
-
- 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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- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
the invention belongs to the technical field of fuel oil desulfurization, and relates to a preparation method of an oleophylic magnetic carbon material loaded molybdenum oxide catalyst, which comprises the steps of firstly preparing magnetic nanoparticles, then synthesizing a magnetic polymer carrier, dissolving the magnetic polymer carrier and the molybdenum-containing precursor in every 20mL of acetonitrile according to the loading amount of the molybdenum-containing precursor being 1-50 wt%, stirring for 1-8 h at 30-70 ℃, calcining for 1-5 h at 500-800 ℃ in a nitrogen atmosphere of a tubular furnace to obtain the catalystMoO x and/MC. The catalyst prepared by the method has small specific surface area, has the advantages of high activity and easy separation of a heterogeneous catalyst, and can improve the yield of oil products; air or oxygen is used as an oxidant, the sulfur removal rate is high, and the requirement of deep desulfurization is met. Compared with the traditional method, the method has the advantages of high desulfurization rate, high efficiency, simple reaction system, mild reaction conditions, easy separation and the like. The catalyst has excellent cycle performance, the activity is basically kept unchanged after the catalyst is circularly used for seven times, and ultra-deep desulfurization can still be realized.
Description
Technical Field
The invention belongs to the technical field of fuel oil desulfurization, and relates to a preparation method of an oleophylic magnetic carbon material loaded molybdenum oxide catalyst and an application of the catalyst in oxidative desulfurization.
Background
The sulfur compounds in the fuel oil are converted to the corresponding SO after combustionxAnd (2) the method causes environmental pollution, and can reduce the utilization efficiency of fuel and increase the emission of PM 2.5. In recent years, due to the increase of environmental problems, ultra-deep desulfurization of fuel has attracted global attention, and strict regulations are established in each country to limit the S content in transportation fuel to 10ppm or less. Because the Hydrodesulfurization (HDS) technology commonly used in the industry at present is a high-energy consumption process and requires conditions of high temperature, high pressure, large hydrogen consumption and the like; and the removal rate of sulfides such as Benzothiophene (BT) and derivatives thereof is not high, and the octane number of oil products is reduced when the corresponding sulfides are removed, so that the search for deep desulfurization technology for replacing HDS is urgently needed. The non-HDS processes have been studied with a major focus on extraction, oxidation, adsorption desulfurization, etc., of which Oxidative Desulfurization (ODS) is considered to be one of the most promising processes due to its high efficiency for heterocyclic sulfide removal.
carbon materials have many excellent characteristics such as cheapness, no toxicity, chemical stability, and excellent conductivity, and their physical interaction mainly involves p-p interaction. The surface of the carbon material is adjusted and modified, so that thiophene compounds can be selectively captured, and the carbon material has better oleophylic property. The magnetic catalyst is a good heterogeneous catalyst because of its easy separation. A great deal of literature indicates that metal oxide activated hydrogen peroxide is also one of the hot spots of oxidative desulfurization research at present, but molybdenum oxide activated air is relatively less used for oxidative desulfurization research.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to disclose a preparation method of an oleophylic magnetic carbon material loaded molybdenum oxide catalyst.
According to the invention, through the configuration design of the catalyst, the carrier of the catalyst is an oleophylic magnetic carbon material, the contact probability with a substrate and an oil phase is enhanced during reaction, and the separation of the catalyst is easy to realize after the reaction.
A preparation method of an oleophylic magnetic carbon material loaded molybdenum oxide catalyst comprises the following steps:
(1) Synthesis of Magnetic Nanoparticles (MNs)
Weighing ferric trichloride hexahydrate and sodium acetate, adding the ferric trichloride hexahydrate and the sodium acetate into ethylene glycol, mixing and stirring uniformly, transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 8 hours at 200 ℃, naturally cooling to normal temperature, washing a solid (MS) for a plurality of times by using deionized water and absolute ethyl alcohol, drying, ultrasonically dispersing the MS into a hydrochloric acid solution, adding water, absolute ethyl alcohol and ammonia water, performing ultrasonic treatment for 0.5 hour, then performing mechanical stirring, simultaneously adding tetraethyl silicate [ TEOS ], reacting for 6 hours at 25 ℃, washing and drying to obtain Magnetic Nanoparticles (MNs);
Wherein the mass volume ratio of ferric trichloride hexahydrate to sodium acetate to glycol to hydrochloric acid is 1.35 g: 3.6 g: 50mL of: 50 mL;
The mass volume ratio of the water to the absolute ethyl alcohol to the ammonia water to the tetraethyl silicate is 20 mL: 80mL of: 1mL of: 0.2 mL;
The concentration of the hydrochloric acid solution is 0.1mol/L, and the mass percentage concentration of ammonia water is 25-28%;
(2) Synthesis of magnetic Polymer Supports
Adding the MNS into a solution containing water, absolute ethyl alcohol and ammonia water, uniformly dispersing by ultrasonic, dropwise adding Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the temperature at 50 ℃ for 48 hours, washing, separating and drying the obtained product by using methanol, adding Azobisisobutyronitrile (AIBN) and 1-vinylimidazole (vim), adding 20mL of toluene as a solvent, reacting for 12 hours at 70 ℃, cleaning by using ethyl acetate, drying for 12 hours at 80 ℃ in vacuum to obtain the magnetic polymer carrier,
wherein the mass-volume ratio of MNS, water, absolute ethyl alcohol, ammonia water and MPS is 0.1-1 g: 5mL of: 15mL of: 0.3 mL: 0.1-1 g, preferably 0.1 g: 5mL of: 15mL of: 0.3 mL: 1g of a compound;
the dosage of the AIBN is 1-10% of the weight of vim, and the dosage of vim is 1-3 g;
The mass percentage concentration of the ammonia water is 25-28%;
(3) Catalyst MoOxsynthesis of/MC
According to the molybdenum-containing precursor loading of 1-50 wt%, dissolving the magnetic polymer carrier and the molybdenum-containing precursor in each 20mL of acetonitrile, stirring at 30-70 ℃ for 1-8 h, preferably stirring at 50 ℃ for 3h, drying, calcining at 500-800 ℃ for 1-5 h, preferably calcining at 600 ℃ for 3h in a tubular furnace nitrogen atmosphere to obtain the catalyst MoOx/MC; wherein the molybdenum-containing precursor comprises a molybdenum-containing inorganic salt or a molybdenum-containing organic salt.
Further, the molybdenum-containing inorganic salt includes phosphomolybdic acid, ammonium molybdate, sodium molybdate, and the like; the organic salt containing molybdenum comprises quaternary ammonium salt, quaternary phosphonium salt or imidazole salt and the like as cation, and phosphomolybdic acid anion or molybdic acid anion and the like as anion.
The loading capacity of the molybdenum-containing precursor is the mass ratio of the molybdenum-containing precursor to the magnetic polymer carrier.
The invention also aims to use the prepared oleophylic magnetic carbon material loaded molybdenum oxide catalyst for oxidative desulfurization of fuel oil.
Laboratory simulation:
The catalyst MoO prepared by the inventionxThe method comprises the following steps of putting the model oil in the MC, introducing air or oxygen, stirring and reacting at a certain temperature, separating an upper oil phase after the reaction is finished, namely the desulfurized oil product, analyzing the sulfur content in the model oil by using a gas chromatography, and calculating the desulfurization rate.
The catalyst MoOxin/MC, MoOxThe air may be activated.
The dosage ratio of the catalyst to the model oil is 0.005-0.02 g: 20mL, the model oil contains aliphatic sulfide or aromatic sulfide, and the sulfur content is 50-1000 ppm.
the flow rate of the air or the oxygen is 50-200 mL/min.
In the reaction, the stirring speed is 500-1500 rpm, the reaction temperature is 110-150 ℃, and the reaction time is 3-8 h.
The desulfurization rate calculation formula is as follows:
The catalyst prepared by the invention can be used for catalytic oxidation removal of aliphatic sulfides and aromatic sulfides in fuel oil, such as Dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-DMDBT), 4, 6-dimethyl dibenzothiophene (4,6-DMDBT), wherein the oxidation reaction of Dibenzothiophene (DBT) can be represented by the following equation:
Advantageous effects
The catalyst prepared by the method has small specific surface area, belongs to a non-porous material, and can improve the yield of oil products; air or oxygen is used as an oxidant, so that the sulfur removal rate is high, the efficiency is high, and the requirement of deep desulfurization can be met under the optimal reaction condition; the catalyst has the advantages of high activity and easy separation of heterogeneous catalyst. Compared with the traditional method, the method has the advantages of high desulfurization rate, high efficiency, simple reaction system, mild reaction conditions, easy separation and the like. The method has mild reaction conditions, does not need pressurizing equipment and is simple to operate; the catalyst and the reaction system are easy to separate after the reaction is finished, the separation can be realized by an external magnetic field or a magnet, the catalyst is convenient to circulate and has no influence on the human body and the environment; the catalyst has excellent cycle performance, the activity is basically kept unchanged after seven cycles of use, and ultra-deep desulfurization can be still realized.
Drawings
FIG. 1 is a graph showing the experimental contact angle of a catalyst.
FIG. 2 XPS plot of catalyst.
FIG. 3 MS (a) and MoOxVSM plot of/MC (b).
FIG. 4 shows a dispersion (a) of the catalyst in ethanol and a photograph (b) of the catalyst separated by a magnet.
FIG. 5 cycle performance testing of the catalyst.
figure 6. nitrogen adsorption desorption curve of catalyst.
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.
Preparation of oil products: dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT) and 4, 6-dimethyl dibenzothiophene (4,6-DMDBT) are respectively dissolved in dodecane, the sulfur content of an oil prepared from DBT is 50-1000 ppm, the sulfur content of an oil prepared from 4-MDBT is 50-1000 ppm, and the sulfur content of an oil prepared from 4,6-DMDBT is 50-1000 ppm.
The preparation method of the magnetic nanoparticles comprises the following steps:
1.35g FeCl was weighed3·6H2Adding O and 3.6g of sodium acetate into a 50mL ethylene glycol beaker, mixing and stirring for 30min, pouring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, and placing the hydrothermal reaction kettle in an oven at 200 ℃ for 8 h; cooling to normal temperature, washing the solid (MS) with absolute ethyl alcohol and deionized water for three times respectively, dispersing the MS into 50mL of 0.1mol/L hydrochloric acid solution after drying, carrying out ultrasonic treatment for 10min, washing with distilled water for several times to remove surface impurities, then adding 20mL of water, 80mL of absolute ethyl alcohol and 1mL of ammonia water, carrying out ultrasonic treatment for half an hour, then carrying out mechanical stirring, simultaneously adding 0.2mL of TEOS, keeping the temperature at 25 ℃ for 6h, washing with distilled water and absolute ethyl alcohol for three times respectively, and drying to obtain Magnetic Nanoparticles (MNs).
Example 1
Weighing 0.1g of MNs, adding the MNs into a solution containing 5mL of water, 15mL of absolute ethyl alcohol and 0.3mL of ammonia water, ultrasonically dispersing the solution for 10min, dropwise adding 0.1g of Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the temperature at 50 ℃ for 48h, washing, separating and drying an obtained product by using methanol, adding 0.1g of Azobisisobutyronitrile (AIBN) and 1g of 1-vinylimidazole (vim), adding 15mL of toluene as a solvent, reacting at 70 ℃ for 12h, washing three times by using ethyl acetate, and keeping the mixture in a vacuum drying oven at 80 ℃ for 12h to obtain the magnetic polymer carrier.
0.2g of the magnetic polymer carrier prepared above and 0.04g of H were weighed3PMo12O40·14H2placing O (HPMo) in 20mL of acetonitrile, stirring at 70 ℃ for 1h, drying at 70 ℃, placing in a nitrogen atmosphere, raising the temperature to 600 ℃ at 5 ℃/min, and treating for 5h to obtain the oleophylic magnetic carbon material-loaded molybdenum oxide catalyst (the load of phosphomolybdic acid is 20%).
To three 100mL round bottom flasks were added 20mL DBT, 4-MDBT and 4,6-DMDBT model oils (oil sulfur content 50ppm), followed by 0.01g catalyst prepared above, 100mL/min O2Magnetically stirring at 1000rpm at 120 deg.C for 6 hr, separating model oil, and detecting DBT, 4-MDBT and 4,6-DMDBT contents in the oil by GC-FID (internal standard method) respectively, wherein the sulfur removal rates are 99.8%, 97.6% and 96.0% respectively.
The successful synthesis of the lipophilic catalyst can be seen from figure 1;
the high resolution peak separation spectrum of molybdenum from FIG. 2 shows the presence of three sets of signal peaks 232.1eV and 236.1eV, 234.2eV and 231.2eV, 232.9eV and 229.6eV, indicating MoOxthe method successfully synthesizes the molybdenum catalyst containing different valence states;
It can be seen from fig. 3 that both substances have superparamagnetism, which makes them easy to separate under an external magnetic field. Their saturation magnetizations were 33.5 and 2.6emu g, respectively-1MoO, in contrast to MSxThe large reduction in the magnetic properties of the/MC may be due to the encapsulation of the carbon material.
Example 2
Weighing 1g of MNs, adding the MNs into a solution containing 5mL of water, 15mL of absolute ethyl alcohol and 0.3mL of ammonia water, ultrasonically dispersing the solution for 10min, dropwise adding 1g of Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the solution at 50 ℃ for 48h, washing, separating and drying an obtained product by using methanol, adding 0.1g of Azobisisobutyronitrile (AIBN) and 3g of 1-vinylimidazole (vim), adding 15mL of toluene as a solvent, reacting at 70 ℃ for 12h, washing three times by using ethyl acetate, and keeping the reaction product in a vacuum drying oven at 80 ℃ for 12h to obtain a magnetic polymer carrier;
Weighing 0.2g of the prepared magnetic polymer carrier and 0.04g of tetrabutylammonium phosphomolybdate, placing the tetrabutylammonium phosphomolybdate in 20mL of acetonitrile, stirring at 30 ℃ for 8h, drying at 70 ℃, placing the mixture in a nitrogen atmosphere, raising the temperature to 600 ℃ at 5 ℃/min, and treating for 1h to obtain the oleophylic magnetic carbon material-loaded molybdenum oxide catalyst (the loading of phosphomolybdic acid is 20%).
To three 100mL round bottom flasks were added 20mL of DBT model oil (oil sulfur content 500ppm), followed by 0.01g of the prepared catalyst, 50mL/min O2Respectively stirring at 110 deg.C, 120 deg.C and 150 deg.C under 500rpm magnetic force for 6h, separating model oil, respectively (internal standard method) detecting DBT content in oil by GC-FID, and calculating sulfur removal rates to be 24.1%, 99.90% and 99.90%.
example 3
Weighing 1g of MNs, adding the MNs into a solution containing 5mL of water, 15mL of absolute ethyl alcohol and 0.3mL of ammonia water, ultrasonically dispersing the solution for 10min, dropwise adding 1g of Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the solution at 50 ℃ for 48h, washing, separating and drying an obtained product by using methanol, adding 0.1g of Azobisisobutyronitrile (AIBN) and 3g of 1-vinylimidazole (vim), adding 15mL of toluene as a solvent, reacting at 70 ℃ for 12h, washing three times by using ethyl acetate, and keeping the reaction product in a vacuum drying oven at 80 ℃ for 12h to obtain a magnetic polymer carrier;
0.2g of the magnetic polymer carrier was weighed, and 0.002g, 0.01g, 0.02g, and 0.1g of H were weighed3PMo12O40·14H2O (HPMo) is placed in 20mL of acetonitrile, stirred at 30 ℃ for 8h, dried at 70 ℃, and placed in a nitrogen atmosphere to be heated to 600 ℃ at the speed of 5 ℃/min for treatment for 1h to obtain the oleophylic magnetic carbon material-loaded molybdenum oxide catalysts with different loading amounts.
To five 100mL round bottom flasks were added 20mL of DBT model oil (oil sulfur content 1000ppm), followed by 0.005g of the prepared catalyst (phosphomolybdic acid supported on a support)Amounts of 1%, 5%, 10%, and 50%), 100mL/min O, respectively2And magnetically stirring at 120 deg.C for 6 hr to separate model oil, and detecting DBT content in the oil by GC-FID (internal standard method) to obtain sulfur removal rates of 68.6%, 96.4%, 95.1%, 99.8% and 97.4%, respectively.
Example 4
Weighing 1g of MNs, adding the MNs into a solution containing 5mL of water, 15mL of absolute ethyl alcohol and 0.3mL of ammonia water, ultrasonically dispersing the solution for 10min, dropwise adding 1g of Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the solution at 50 ℃ for 48h, washing, separating and drying an obtained product by using methanol, adding 0.05g of Azobisisobutyronitrile (AIBN) and 3g of 1-vinylimidazole (vim), adding 15mL of toluene as a solvent, reacting at 70 ℃ for 12h, washing three times by using ethyl acetate, and keeping the reaction product in a vacuum drying oven at 80 ℃ for 12h to obtain a magnetic polymer carrier;
weighing 0.2g of the prepared magnetic polymer carrier and 0.04g of ammonium molybdate, placing the ammonium molybdate in 20mL of acetonitrile, stirring at 50 ℃ for 3h, drying at 70 ℃, placing the mixture in a nitrogen atmosphere, and treating at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ at a speed of 5 ℃/min for 1h to obtain the oleophylic magnetic carbon material-loaded molybdenum oxide catalyst (the load of phosphomolybdic acid is 20%).
20mL of DBT model oil (the sulfur content of the oil is 200ppm) is added into four 100mL round-bottomed flasks, then 0.02g of the prepared catalyst is added, the reaction temperature is 120 ℃, the calcination temperature is 500 ℃, 600 ℃, 700 ℃ and 800 ℃, the mixture is magnetically stirred at 1500rpm for 6 hours, the model oil is separated, the DBT content in the oil is detected by adopting GC-FID (internal standard method), and the sulfur removal rates are 45.5%, 99.8%, 97.7% and 96.0% respectively through calculation.
Example 5
Weighing 0.1g of MNs, adding the MNs into a solution containing 5mL of water, 15mL of absolute ethyl alcohol and 0.3mL of ammonia water, ultrasonically dispersing the solution for 10min, dropwise adding 0.1g of Methacryloxypropyltrimethoxysilane (MPS) under mechanical stirring, keeping the temperature at 50 ℃ for 48h, washing, separating and drying an obtained product by using methanol, adding 0.05g of Azobisisobutyronitrile (AIBN) and 3g of 1-vinylimidazole (vim), adding 15mL of toluene as a solvent, reacting at 70 ℃ for 12h, washing three times by using ethyl acetate, and keeping the mixture in a vacuum drying oven at 80 ℃ for 12h to obtain a magnetic polymer carrier;
Weighing 0.2g of the prepared magnetic polymer carrier and 0.04g of ammonium molybdate, placing the ammonium molybdate in 20mL of acetonitrile, stirring at 50 ℃ for 3h, drying at 70 ℃, placing the mixture in a nitrogen atmosphere, raising the temperature to 600 ℃ at 5 ℃/min, and treating for 2h to obtain the oleophylic magnetic carbon material-loaded molybdenum oxide catalyst (the load of phosphomolybdic acid is 20%).
to three 100mL round bottom flasks were added 20mL of DBT model oil (oil sulfur content 200ppm), followed by 0.01g of the catalyst prepared above, 200mL/min O2and respectively magnetically stirring at 1000rpm for 3h, 6h and 8h at 120 ℃, separating model oil, detecting the DBT content in the oil by adopting a GC-FID (internal standard method), and respectively calculating the sulfur removal rates to be 95.2%, 99.8% and 99.9%.
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 an oleophylic magnetic carbon material loaded molybdenum oxide catalyst is characterized by comprising the following steps:
(1) synthesis of magnetic nanoparticle MNs
Weighing ferric trichloride hexahydrate and sodium acetate, adding the ferric trichloride hexahydrate and the sodium acetate into ethylene glycol, mixing and stirring uniformly, transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 8 hours at 200 ℃, naturally cooling to normal temperature, washing solid MS for a plurality of times by using deionized water and absolute ethyl alcohol, drying, ultrasonically dispersing the MS into a hydrochloric acid solution, adding water, absolute ethyl alcohol and ammonia water, performing ultrasonic treatment for 0.5 hour, performing mechanical stirring, simultaneously adding tetraethyl silicate, reacting for 6 hours at 25 ℃, washing and drying to obtain magnetic nano particles MNs;
Wherein the mass volume ratio of ferric trichloride hexahydrate to sodium acetate to glycol to hydrochloric acid is 1.35 g: 3.6 g: 50mL of: 50 mL;
The mass volume ratio of the water to the absolute ethyl alcohol to the ammonia water to the tetraethyl silicate is 20 mL: 80mL of: 1mL of: 0.2 mL;
The concentration of the hydrochloric acid solution is 0.1mol/L, and the mass percentage concentration of ammonia water is 25-28%;
(2) Synthesis of magnetic Polymer Supports
adding the MNS into a solution containing water, absolute ethyl alcohol and ammonia water, uniformly dispersing by ultrasonic, dropwise adding methacryloxypropyltrimethoxysilane MPS under mechanical stirring, keeping the temperature at 50 ℃ for 48 hours, washing, separating and drying the obtained product by using methanol, adding azobisisobutyronitrile AIBN and 1-vinyl imidazole vim, adding 20mL of toluene as a solvent, reacting for 12 hours at 70 ℃, cleaning by using ethyl acetate, drying for 12 hours at 80 ℃ in vacuum to obtain the magnetic polymer carrier,
wherein the mass-volume ratio of MNS, water, absolute ethyl alcohol, ammonia water and MPS is 0.1-1 g: 5mL of: 15mL of: 0.3 mL: 0.1-1 g;
The dosage of the AIBN is 1-10% of the weight of vim, and the dosage of vim is 1-3 g;
The mass percentage concentration of the ammonia water is 25-28%;
(3) Catalyst MoO x synthesis of/MC
dissolving the magnetic polymer carrier and the molybdenum-containing precursor in every 20mL of acetonitrile according to the loading amount of the molybdenum-containing precursor being 1-50 wt%, stirring at 30-70 ℃ for 1-8 h, drying, and calcining at 500-800 ℃ in a nitrogen atmosphere of a tubular furnace for 1-5 h to obtain the catalyst MoO x The molybdenum-containing precursor comprises molybdenum-containing inorganic salt or molybdenum-containing organic salt.
2. The method for preparing the oleophilic magnetic carbon material-supported molybdenum oxide catalyst according to claim 1, wherein the method comprises: in the step (2), the mass-to-volume ratio of MNS, water, absolute ethyl alcohol, ammonia water and MPS is 0.1 g: 5mL of: 15mL of: 0.3 mL: 1g of the total weight of the composition.
3. The method for preparing the oleophilic magnetic carbon material-supported molybdenum oxide catalyst according to claim 1, wherein the method comprises: and (3) dissolving the magnetic polymer carrier and the molybdenum-containing precursor in each 20mL of acetonitrile, and stirring for 3h at 50 ℃.
4. the method for preparing the oleophilic magnetic carbon material-supported molybdenum oxide catalyst according to claim 1, wherein the method comprises: and (3) calcining for 3h at 600 ℃ in a nitrogen atmosphere of a tube furnace.
5. the method for preparing the oleophilic magnetic carbon material-supported molybdenum oxide catalyst according to claim 1, wherein the method comprises: the inorganic salt containing molybdenum in the step (3) comprises phosphomolybdic acid, ammonium molybdate and sodium molybdate.
6. The method for preparing the oleophilic magnetic carbon material-supported molybdenum oxide catalyst according to claim 1, wherein the method comprises: in the step (3), the molybdenum-containing organic salt is cation comprising quaternary ammonium salt, quaternary phosphonium salt and imidazole salt, and anion comprising phosphomolybdate anion and molybdate anion.
7. An oleophilic magnetic carbon material-supported molybdenum oxide catalyst prepared according to the method of any one of claims 1 to 6.
8. The use of the oleophilic magnetic carbon material-supported molybdenum oxide catalyst as claimed in claim 7, wherein: the method is applied to the oxidation desulfurization of fuel oil.
9. The use of the oleophilic magnetic carbon material-supported molybdenum oxide catalyst as claimed in claim 8, wherein: the catalyst can remove aliphatic sulfides and aromatic sulfides in fuel oil by catalytic oxidation.
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| CN113499782A (en) * | 2021-07-30 | 2021-10-15 | 江苏大学 | Preparation of hollow mesoporous silica dissolved regeneration limited-area cobalt molybdate catalyst and catalytic oxidation diesel oil desulfurization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| WEI JIANG, ET AL: "Polyoxometalate-Based Poly(ionic liquid) as a Precursor for Superhydrophobic Magnetic Carbon Composite Catalysts toward Aerobic Oxidative Desulfurization", 《ACS SUSTAINABLE CHEM. ENG.》 * |
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| CN112588286A (en) * | 2020-12-11 | 2021-04-02 | 江苏大学 | Preparation method and application of carbon nanotube modified molybdenum-doped tungsten oxide catalyst |
| CN113499782A (en) * | 2021-07-30 | 2021-10-15 | 江苏大学 | Preparation of hollow mesoporous silica dissolved regeneration limited-area cobalt molybdate catalyst and catalytic oxidation diesel oil desulfurization method |
| CN113499782B (en) * | 2021-07-30 | 2024-03-01 | 江苏大学 | Preparation method of hollow mesoporous silica dissolution regeneration limited-domain cobalt molybdate catalyst and catalytic oxidation diesel desulfurization method |
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