CN110747004A - Application of spinel ferrite magnetic nano catalyst in oil product desulfurization - Google Patents
Application of spinel ferrite magnetic nano catalyst in oil product desulfurization Download PDFInfo
- Publication number
- CN110747004A CN110747004A CN201911122038.5A CN201911122038A CN110747004A CN 110747004 A CN110747004 A CN 110747004A CN 201911122038 A CN201911122038 A CN 201911122038A CN 110747004 A CN110747004 A CN 110747004A
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- CN
- China
- Prior art keywords
- desulfurization
- catalyst
- magnetic nano
- use according
- oil product
- Prior art date
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Links
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 77
- 230000023556 desulfurization Effects 0.000 title claims abstract description 77
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 19
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 18
- 239000011029 spinel Substances 0.000 title claims abstract description 18
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 229910000708 MFe2O4 Inorganic materials 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 229910018965 MCl2 Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000000605 extraction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001869 inorganic persulfate Inorganic materials 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000000696 magnetic material Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229910003321 CoFe Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 description 1
- 229910016516 CuFe2O4 Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 150000004976 peroxydisulfates Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/18—Halogen-containing compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/33—
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/22—Compounds containing sulfur, selenium, or tellurium
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/24—Phosphorus-containing compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention relates toThe invention discloses an application of spinel ferrite magnetic nano catalyst in oil product desulfurization, belonging to the field of petrochemical industry2+And Fe3+Chloride of (4) to produce MFe2O4The prepared catalyst is firm in structure, resistant to high temperature and not easy to agglomerate; the catalyst is used for the oxidation extraction desulfurization process, and has high reaction activity, good desulfurization effect, convenient recovery and good catalyst recycling effect; not only can catalyze the oxidation extraction desulfurization process which takes hydrogen peroxide as an oxidant, but also can catalyze the desulfurization process which takes simple and easily obtained inorganic persulfate as an oxidant directly.
Description
Technical Field
The invention belongs to the technical field of oil product desulfurization in the field of petrochemical industry, and particularly relates to preparation of a spinel ferrite magnetic nano catalyst and application of the spinel ferrite magnetic nano catalyst in oil product desulfurization.
Background
With the rapid development of economy, the usage amount of fuel oil is increasing, and the pollution problem caused by the fuel oil is puzzling, so in recent years, the research on the problems of fuel oil desulfurization and the like is not interrupted. Studies have shown that 1/3 of sulfur in air is derived from the combustion and re-emission of automotive fuel. It is well known that the sulfur-containing compounds in fuel oils are varied and include elemental sulfur, hydrogen sulfide, mercaptans, sulfides, cyclic sulfides, disulfides, thiophenes and homologs thereof, and the like. The sulfides are combusted to generate sulfur oxides, and the sulfur oxides are released into the air to cause certain damage to vegetation, water bodies, soil and other buildings in the nature. The generated sulfur dioxide meets water vapor in the air to form acid rain, and has a strong promoting effect on the formation of inhalable particles which are generated along with the combustion process of the fuel, so that severe weather such as haze and the like can be caused, the haze can damage the respiratory system of people, and even can induce related systems to generate canceration. The presence of sulfides in fuel oil can also poison catalysts in vehicle exhaust purifiers, which can hinder the removal of pollutants from engine exhaust. The sulfide becomes acidic and corrodes the engine, resulting in a reduction in the service life of the engine and a reduction in the use value of automobiles and the like. The high content of sulfides in fuel oils also limits the industrial application of highly new fuel technologies such as fuel cells and internal combustion engines. Therefore, it is important to reduce the sulfur content in fuel oil before specific application and effectively improve air pollution.
Magnetic materials are generally considered to be substances that directly or indirectly generate magnetism, such as iron, cobalt, nickel, or alloys thereof, which are transition metal elements. As an old and traditional functional material, magnetic materials have been widely used in many aspects of our lives, such as iron core materials used in transformers, magnetic disk soft and hard disks used for storing records, sensors, and the like. Magnetic materials can be classified into soft magnetic materials and hard magnetic materials according to the ease of demagnetization after magnetization. Those that are easily demagnetized are called soft magnetic materials, while those that are difficult to demagnetize are called hard magnetic materials. In the traditional sense, the nano material refers to a material with at least one dimension in a three-dimensional space within a range of 1-100 nanometers. Magnetic nanoparticles are a main direction for the development of magnetic nanomaterials at present, and have attracted extensive attention due to their unique characteristics and advantages. Because the particle size is in the nanometer level, the magnetic nano material not only has the characteristics of the nano material, but also has other special magnetic properties, such as superparamagnetism, giant magnetoresistance effect, magnetic anisotropy and good wave-absorbing property. Magnetic nanoparticles are novel materials which are developed rapidly and have high application value at present, are closely related to various aspects of informatization, automation, national defense and national economy, and have more and more applications in various scientific fields such as biomedicine, magnetic fluid, wave-absorbing materials, catalysis, nuclear magnetic resonance imaging, data storage, environmental protection and the like.
Inorganic persulfates, including peroxosulfates and peroxodisulfates, are widely used in environmental cleanup, redox and polymerization reactions due to their low cost, ready availability, ease of transportation, and potential electrochemical renewability. In the above reaction, highly reactive sulfate radicals (SO 4. -) having a high oxidation potential (2.5-3.1V) are typical active oxidants. Such radicals are generated by cleaving the peroxy bonds of peroxymonosulfates and peroxydisulfates. However, persulfates are thermodynamically strong oxidizers which react too slowly directly and therefore require activation, especially inorganic persulfates. Common activation means are catalytic activation, external heat and electrochemical activation. In order to realize an efficient and mild process of directly utilizing simple and easy inorganic persulfate, research on different metal catalysts has been paid extensive attention.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide spinel ironThe application of the ferrite magnetic nano catalyst in oil product desulfurization. The invention first utilizes coprecipitation M2+And Fe3+Chloride of (4) to produce MFe2O4The prepared catalyst is firm in structure, resistant to high temperature and not easy to agglomerate; the catalyst is used for the oxidation extraction desulfurization process, and has high reaction activity, good desulfurization effect, convenient recovery and good catalyst recycling effect; not only can catalyze the oxidation extraction desulfurization process which takes hydrogen peroxide as an oxidant, but also can catalyze the desulfurization process which takes simple and easily obtained inorganic persulfate as an oxidant directly.
In order to achieve the purpose, the invention adopts the specific scheme that:
the invention provides an application of the spinel ferrite magnetic nano catalyst in oil product desulfurization.
As a further optimization of the application, the method for desulfurizing oil products by using the spinel ferrite magnetic nano catalyst comprises the following steps:
step one, at room temperature, every 10mmol of FeCl3·6H2O and 5-5.5 mmol MCl2·6H2Mixing O in 50-100 mL of ethylene glycol to obtain a clear solution; adding 3.5-7.5 g of NaAc and 0.8-2.0 g of polyethylene glycol into the clear solution to obtain a mixture; violently stirring the mixture for 20-40 min to enable the mixture solution to become clear again, then sealing the mixture solution in a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, heating the high-pressure kettle to 200 ℃ and keeping the temperature for 8-72h, and then cooling the high-pressure kettle to room temperature to obtain a black product; washing the black product with ethanol and drying at 60 deg.C for 4-8h to obtain spinel ferrite magnetic nanometer MFe2O4Catalyst for standby;
step two, 0.04g of the magnetic nano MFe prepared in the step one2O4Mixing a catalyst, 0.8-1.2g of an extracting agent and 2.5-4.0g of an oil product to be desulfurized to obtain a mixed solution; then 0.1-1g of oxidant is added, and the mixture reacts for 1-2h at 40-80 ℃ under the condition of stirring, thus completing the desulfurization;
step three, standing and layering the desulfurization system reacted in the step two to obtain a desulfurized oil product; the catalyst at the lower layer can be directly added into the step two again to be oxidized and extracted and coupled with the oil product to be desulfurized for desulfurization after being simply and magnetically adsorbed, washed and dried, thereby achieving the recycling of the spinel ferrite magnetic nano catalyst.
As a further optimization of the process, in step one, MCl2·6H2M in O is any one of Co, Ni, Zn, Cu and Mn.
As a further optimization of the method, in the second step, the extractant is any one or a mixture of several of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hydrogen sulfate, water, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, pyrrole and furan. Preferably, 1-butyl-3-methylimidazolium tetrafluoroborate and N, N-dimethylformamide are used as extracting agents.
As a further optimization of the process, in step two, the oxidizing agent includes, but is not limited to, K2S2O8、Na2S2O8、（NH4）2S2O8、KHSO5、H2O2Or [ Cnmin]2[S2O8]（n=1~10）。
As a further optimization of the method, in the third step, the washing and drying are carried out, water and ethanol are adopted for washing, and the temperature during drying is 60-100 ℃.
Has the advantages that:
1. the invention utilizes coprecipitation M2+And Fe3+Chloride of (4) to produce MFe2O4And (M = Co, Ni, Zn, Cu, Mn) and other ferrite magnetic nano-catalysts are applied to the oxidation extraction desulfurization process, and have the characteristics of higher stability and easiness in recovery from a reaction system. The spinel ferrite magnetic nano catalyst is used for catalytic oxidation extraction desulfurization, and has high catalytic desulfurization efficiency and magnetismSimple separation and recovery, long service life and the like.
2. Spinel CoFe prepared by the invention2O4Magnetic nano desulfurization catalyst and K2S2O8After the oxidant and the N, N-dimethylformamide are combined for use, the excellent desulfurization effect and the service life are shown at the temperature of 60 ℃. It was determined to be at 60oUnder the condition of C, the initial sulfur content of the fuel oil is 1000ppm, the desulfurization rate is up to more than 93% within 120min, the desulfurized oil product is obtained after standing and layering, the lower-layer catalyst can still be recycled after magnetic adsorption and simple washing and drying, the desulfurization rate is still more than 90% after 7 times of cyclic use, and the desulfurization effect is obvious. Compared with hydrogen peroxide as oxidant, the potassium persulfate oxidant in powder form is selected, so that the required O/S ratio is lower, and the specific implementation modes of economy, stability, safety and simple and convenient operation are realized
The invention utilizes coprecipitation M2+And Fe3+Chloride of (4) to produce MFe2O4Ferrite magnetic nano-catalyst (M = Co, Ni, Zn, Cu, Mn) and the like, and is applied to the oxidation extraction desulfurization process, and comprises the following steps:
step one, taking 10mmol FeCl at room temperature3·6H2O and (5-5.5) mmol MCl2·6H2Mixing O in ethylene glycol to obtain a clear solution, adding NaAc (3.5-7.5 g) and polyethylene glycol (0.8-2.0 g), vigorously stirring the mixture for 20-40 min to make the obtained solution clear again, sealing in a stainless steel autoclave (100 ml capacity) with a polytetrafluoroethylene lining, heating the autoclave to 200 ℃ and keeping the temperature for 8-72h, cooling to room temperature, washing a black product with ethanol for several times, and drying at 60 ℃ for 4-8h to obtain the spinel ferrite magnetic nano MFe2O4Catalyst for standby;
step two, 0.8-1.2g of extracting agent and 0.04g of magnetic nano MFe prepared in the step one2O4Mixing the catalyst with 2.5-4.0g of fuel oil to obtain a mixed solution; then 0.1-1g of oxidant is added, and the mixture reacts for 1-2h at 40-80 ℃ under the stirring condition, thus completing the desulfurization for standby;
step three, standing and layering the desulfurization system reacted in the step two to obtain a desulfurized oil product; the catalyst at the lower layer can be directly added into the step two again to be oxidized and extracted and coupled with the oil product to be desulfurized for desulfurization after being simply and magnetically adsorbed, washed and dried, thereby achieving the recycling of the spinel ferrite magnetic nano catalyst.
In the first step, the volume of the glycol is 50-100 ml.
In the second step, the extractant is ionic liquid with extractant action, which has different anions and cations, such as 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hydrogen sulfate and the like; and one or more of water, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, pyrrole and furan, wherein 1-butyl-3-methylimidazolium tetrafluoroborate and N, N-dimethylformamide are preferably used as extractants.
In step two, the catalyst used comprises magnetic nano MFe2O4And a composite catalyst with the same active component. The oxidant includes but is not limited to K2S2O8、Na2S2O8、（NH4）2S2O8、KHSO5、H2O2Or [ Cnmin]2[S2O8]And the material can also be the same structure material.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) Adding 10mmol of FeCl3·H2O and 5mmol CoCl2·6H2Directly dissolving O in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave for sealing, putting the autoclave into a vacuum drying oven,vacuum preserving at 200 deg.C for 8-72h, cooling to room temperature after reaction, centrifuging, washing, drying at 60 deg.C for 6 hr to obtain CoFe2O4；
(2) 1.0g of N, N-dimethylformamide and 0.04g of CoFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4g K was added2S2O8Reacting for 120min at 60 ℃ under the stirring condition, thus finishing the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed, and the cyclic utilization of the catalyst is completed.
It was determined that the desulfurization rate of the fuel oil was 95.3% after the desulfurization treatment by the desulfurization method of this example.
Example 2
(1) Adding 10mmol of FeCl3·H2O and 5mmol NiCl2·6H2Directly dissolving O in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, carrying out vacuum storage for 8-72 hours at 200 ℃, cooling to room temperature after complete reaction, then carrying out centrifugal washing, putting the crude product into a drying oven, and drying for 6 hours at 60 ℃ to obtain NiFe2O4；
(2) 1.0g of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and 0.04g of NiFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4g k was added2S2O8Reacting for 120min at 80 ℃ under the condition of stirring to complete the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was determined that the desulfurization rate of the fuel oil was 65.3% after the desulfurization treatment by the desulfurization method of this example.
Example 3
(1) Adding 10mmol of FeCl3·H2O and 5mmol CoCl2·6H2Directly dissolving O in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, carrying out vacuum storage for 8-72 hours at 200 ℃, cooling to room temperature after complete reaction, then carrying out centrifugal washing, putting the crude product into a drying oven, and drying for 6 hours at 60 ℃ to obtain CoFe2O4；
(2) 1.0g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.04g of CoFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4gk was added2S2O8Reacting for 120min at 80 ℃ under the condition of stirring to complete the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was determined that the desulfurization rate of the fuel oil was 86.1% after the desulfurization treatment by the desulfurization method of this example.
Example 4
(1) Adding 10mmol of FeCl3·H2O and 5mmolZnCl2Directly dissolving in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, preserving the stainless steel autoclave at 200 ℃ in vacuum for 8 to 72 hours, cooling the autoclave to room temperature after complete reaction, then centrifugally washing, putting the crude product into a drying oven, and drying the crude product at 60 ℃ for 6 hours to obtain ZnFe2O4；
（2）1.0g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.04g of ZnFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4gk was added2S2O8Reacting for 120min at 60 ℃ under the stirring condition, thus finishing the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was determined that the desulfurization rate of the fuel oil was 64.6% after the desulfurization treatment by the desulfurization method of this example.
Example 5
(1) Adding 10mmol of FeCl3·H2O and 5mmolCuCl2Directly dissolving in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, preserving the stainless steel autoclave at 200 ℃ in vacuum for 8 to 72 hours, cooling to room temperature after complete reaction, then centrifugally washing, putting the crude product into a drying oven, and drying for 6 hours at 60 ℃ to obtain CuFe2O4；
(2) 1.0g of 1-butyl-3-methylimidazolium hexafluorophosphate and 0.04g of CuFe prepared in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4gK was added2S2O8Reacting for 120min at 60 ℃ under the stirring condition, thus finishing the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was determined that the desulfurization rate of the fuel oil was 63.02% after desulfurization treatment by the desulfurization method of this example.
Example 6
(1) Will 10mmolFeCl3·H2O and 5mmol CoCl2·6H2Directly dissolving O in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, carrying out vacuum storage for 8-72 hours at 200 ℃, cooling to room temperature after complete reaction, then carrying out centrifugal washing, putting the crude product into a drying oven, and drying for 6 hours at 60 ℃ to obtain CoFe2O4；
(2) 1.0g of 1-butyl-3-methylimidazolium hydrogen sulfate and 0.04g of CoFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4g Na was added2S2O8Reacting for 120min at 60 ℃ under the stirring condition, thus finishing the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was found that the desulfurization rate of the fuel oil was 53.0% after the desulfurization treatment by the desulfurization method of this example.
Example 7
(1) Adding 10mmol of FeCl3·H2O and 5mmol CoCl2·6H2Directly dissolving O in a beaker containing 80ml of ethylene glycol, respectively adding 7.2g of NaAc and 2.0g of polyethylene glycol, mixing and stirring for 30 minutes, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave for sealing, putting the stainless steel autoclave into a vacuum drying oven, carrying out vacuum storage for 8-72 hours at 200 ℃, cooling to room temperature after complete reaction, then carrying out centrifugal washing, putting the crude product into a drying oven, and drying for 6 hours at 60 ℃ to obtain CoFe2O4；
(2) 1.0g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.04g of CoFe obtained in step (1)2O4Mixing with 4g of fuel oil having an initial sulfur content of 500ppm to obtain a mixed solution; then 0.4g (NH) was added4)2S2O8Reacting for 120min at 60 ℃ under the stirring condition, thus finishing the desulfurization of the fuel oil;
(3) standing and layering the desulfurization system reacted in the step (2) to obtain a desulfurized oil product; the lower catalyst layer can be directly added into the reaction system again for oxidation-extraction coupling desulfurization after being simply and magnetically adsorbed and washed.
It was found that the desulfurization rate of the fuel oil was 78.6% after the desulfurization treatment by the desulfurization method of this example.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.
Claims (8)
1. The spinel ferrite magnetic nano catalyst is applied to oil product desulfurization.
2. Use according to claim 1, characterized in that: the method for desulfurizing oil by using the spinel ferrite magnetic nano catalyst comprises the following steps:
step one, at room temperature, every 10mmol of FeCl3·6H2O and 5-5.5 mmol MCl2·6H2Mixing O in 50-100 mL of ethylene glycol to obtain a clear solution; adding 3.5-7.5 g of NaAc and 0.8-2.0 g of polyethylene glycol into the clear solution to obtain a mixture; violently stirring the mixture for 20-40 min to enable the mixture solution to become clear again, then sealing the mixture solution in a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, heating the high-pressure kettle to 200 ℃ and keeping the temperature for 8-72h, and then cooling the high-pressure kettle to room temperature to obtain a black product; washing the black product with ethanol and drying at 60 deg.C for 4-8h to obtain spinel ferrite magnetic nanometer MFe2O4Catalyst for standby;
step two, 0.04g of the magnetic nano MFe prepared in the step one2O4Catalyst, 0.8-1.2g extractant and 2.5-4.0g of oil product to be desulfurized is mixed to obtain mixed solution; then 0.1-1g of oxidant is added, and the mixture reacts for 1-2h at 40-80 ℃ under the condition of stirring, thus completing the desulfurization;
step three, standing and layering the desulfurization system reacted in the step two to obtain a desulfurized oil product; the catalyst at the lower layer can be directly added into the step two again to be oxidized and extracted and coupled with the oil product to be desulfurized for desulfurization after being simply and magnetically adsorbed, washed and dried, thereby achieving the recycling of the spinel ferrite magnetic nano catalyst.
3. Use according to claim 2, characterized in that: in step one, MCl2·6H2M in O is any one of Co, Ni, Zn, Cu and Mn.
4. Use according to claim 2, characterized in that: in the second step, the extractant is any one or a mixture of more of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hydrogen sulfate, water, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, pyrrole and furan.
5. Use according to claim 4, characterized in that: the extractant is 1-butyl-3-methylimidazole tetrafluoroborate or N, N-dimethylformamide as the extractant.
6. Use according to claim 2, characterized in that: in step two, the oxidant includes but is not limited to K2S2O8、Na2S2O8、（NH4）2S2O8、KHSO5、H2O2Or [ Cnmin]2[S2O8]。
7. Use according to claim 6, characterized in that: said [ Cnmin]2[S2O8]N =1~ 10.
8. Use according to claim 2, characterized in that: in the third step, washing and drying are carried out, water and ethanol are adopted for washing, and the temperature during drying is 60-100 ℃.
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