CN102585888B - Oxidative desulfurization method for rare earth polyacid and ionic liquid extraction catalysis fuel oil - Google Patents
Oxidative desulfurization method for rare earth polyacid and ionic liquid extraction catalysis fuel oil Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 21
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 19
- 239000000295 fuel oil Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000000605 extraction Methods 0.000 title claims abstract description 7
- 230000023556 desulfurization Effects 0.000 title abstract description 12
- 230000001590 oxidative effect Effects 0.000 title abstract 3
- 238000006555 catalytic reaction Methods 0.000 title abstract 2
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims description 31
- 239000000446 fuel Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- -1 1-butyl-3-methyl imidazolium tetrafluoroborate Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000011964 heteropoly acid Substances 0.000 description 11
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
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- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
The invention discloses an oxidative desulfurization method for rare earth polyacid and ionic liquid extraction catalysis fuel oil, belonging to the technical field of catalytic oxidative desulfurization of fuel oil. Fuel oil with high sulfur content is catalytically oxidized under a catalytic system consisting of rare earth polyoxometallate, an ionic liquid and hydrogen peroxide, so that a deep desulfurization effect is achieved at the normal temperature, and efficient cleaning and utilization of energy are realized. Moreover, a catalyst and the ionic liquid are not degraded after repeated circular reactions, so that the method is a successful desulfurization method. The catalyst used in the catalytic system has the advantages of easiness for preparing, accurate detection measure, short reaction time, high catalytic oxidation transformation ratio and easiness in recycling.
Description
Technical field
The invention belongs to oil fuel catalytic oxidation desulfurization technical field, particularly a kind of method of rare earth polyacid and ion liquid abstraction catalytic fuel oil oxidation sweetening.
Background technology
Sulphur in crude oil and petroleum fractions exists with the form of elementary sulfur, hydrogen sulfide and organic sulfide.Organosulfur compound generally can be divided into thio-alcohol, thioether class, disulfides and thiophene-based, and these S-contained substances are distributed in each distillate in the course of processing of crude oil.Sulfocompound in gasoline be take mercaptan, thioether and monocycle thiophene as main, is mainly derived from FCC gasoline.Sulfocompound in diesel oil distillate has mercaptan, thioether, thiophene, thionaphthene and dibenzothiophene etc., and wherein 4 of dibenzothiophene and 6 while having alkyl to exist, because the steric hindrance of alkyl makes desulfurization more difficult.The sulfocompound of oil product can generate oxysulfide after burning, wherein sulfurous gas most importantly.SOx is discharged in atmosphere and easily forms acid rain, destroys the eubiosis, causes environmental pollution.Although the forming section of China's acid rain is caused by industry and life burning high sulfur coal, the sulfide in vehicle fuel also can not be ignored the pollution that atmosphere causes; The existence of Sulfur content in Fuel Oil simultaneously can make the quantity discharged of objectionable impurities in vehicle exhaust increase, and causes the vehicle exhaust conversion catalyst poisoning, and can produce corrosion to the automobile metal parts.
China's gasoline, diesel oil are compared with the gasoline property of Europe, the U.S., Japan, and principal feature is: sulphur content is higher; Olefin(e) centent is higher; Aromatic hydrocarbons level in oil product is low; The vapour pressure of oil product is higher; Oxygenatedchemicals is low; The octane value irrational distribution.China planning fuel oil quality to 2010 is year in line with international standards, how effectively to remove the oil product medium sulphide content, is to guarantee that the developed countries such as domestic oil refining industry and America and Europe compare competitive basis.Therefore, it is crucial selecting effective doctor treatment.According to the characteristics of oil product institute sulfur compound, the physics or the chemical desulfurization method that adopt at present mainly contain the technology such as shortening, biochemical process, catalytic oxidation, absorption method, solvent extraction.No matter be hydrogenation or the selective hydrogenation treatment technology of raw material, their common ground is all to need High Temperature High Pressure, consumption hydrogen, oil product octane value to reduce.Although selective hydrogenation is selected at catalyzer, in technical process, has carried out many improvement, has avoided a large amount of consumption of hydrogen, loss of octane number reduces, and has improved facility investment and process cost, the not large-area popularization of this technology.So find a kind of operational condition gentleness, sweetening effectiveness is good, environmentally safe, power consumption is few, and investment cost is low, and the sweetening agent that is easy to regenerate is the key of non-hydrogenating desulfurization technology.
Polyacid compound is the poly-metal deoxide that a class contains the metals such as V, Mo, W.By what oxygen acid radical ion of the same race condensation formed, be same polyanionic, isopoly-acid is in its acid.By what the condensation of different types of oxygen acid root negatively charged ion formed, be heteropolyanion, heteropolyacid is in its acid.At present known have the atom of nearly 70 kinds of elements to can be used as the heteroatoms in heteropolyacid, comprise whole First Series transition element, most second and third serial transition element, add B, Al, Ga, Si, Ge, Sn, P, As, Sb, Bi, Se, Te, I etc.And every kind of heteroatoms often can different valence state be present in heteropolyanion, so kind is quite various.Polyacid is the Polyoxometallate with topological framework, in catalytic field, biology, electrode, medicine and Materials science, potential application is arranged all, is called as inorganic polymer.
In recent years, heteropolyacid (salt) has more and more received people's concern as the catalyzer in organic synthesis and petrochemical complex.Heteropolyacid (salt) has advantages of that structure is definite, and the constitutional features of title complex and metal oxide is not only arranged, and acidity and redox property are arranged again; Both can be used as homogeneous phase or heterogeneous catalyst, can be used as again the dual-function catalyst that can transmit simultaneously proton and electronics.In some reaction, the catalytic activity of heteropolyacid (salt) and selectivity surpass composite oxides and molecular sieve.Since the seventies, external existing by the example of heteropoly acid catalyst for suitability for industrialized production, and started gradually the properity of relevant heteropolyacid and the systematic study of katalysis relation.Japan, USSR (Union of Soviet Socialist Republics) are being done a large amount of work aspect the heterogeneous catalyst of heteropoly acid catalyst and homogeneous catalysis respectively.Japan adopts heteropolyacid catalyst in the seventies in propylene hydration production, successfully realized industrialization.Domestic applied research to heteropoly acid catalyst is also progressively carried out.At present, heteropoly acid catalyst has been applied in domestic some chemical plant on acetify reaction and dihydroxyphenyl propane are synthetic, obtained economic benefit and social benefit preferably.
With traditional Keggin type, compare with Wells-Dawson type polyoxoanion, the sandwich-like polyoxoanion has better stability to hydrolysis.This polyoxoanion is preserved in can the aqueous solution at room temperature more than 20 years and is not degraded, simultaneously, can stable existence in the scope of such polyacid pH=6.0～10 in water, with hydrotalcite, good compatibility is arranged.
With traditional molecular solvent, compare, ionic liquid has better thermostability and chemical stability, wider liquid journey, and lower vapour pressure, be suitable for working under comparatively high temps, and multiple organic-inorganic material is had to the good characteristics such as solubleness.Unique is different with anion species according to the positively charged ion that forms ionic liquid, and the physicochemical property of ionic liquid at room temperature have very large difference, can carry out as requested the ionic liquid design in theory.Up to now, ionic liquid is widely used in the fields such as catalytic chemistry, organic synthesis, isolation technique, electrochemistry, Materials science, Polymer Synthesizing and life science as a kind of novel green medium and functional materials.Along with going deep into of research work, the applied research of ionic liquid in chemistry, by the green surrogate of the conventional molecular solvent of initial conduct, progressively design and the application facet to functionalized ion liquid or special-purpose ionic liquid develops.
Summary of the invention
The objective of the invention is the oil fuel of high sulfur-bearing, by catalyzed oxidation under the catalyst system of rare earth polyoxometallate, ionic liquid and hydrogen peroxide coupling, to realize at normal temperatures deep desulfuration, obtained so far in sulfur method sweetening effectiveness comparatively significantly.
Technical scheme of the present invention is that rare earth element is incorporated in the sandwich-like polyacid compound and forms the polyacid compound that contains rare earth, then with ionic liquid, hydrogen peroxide coupling, forms efficient extraction catalytic oxidation desulfurization system, reaches the purpose of oil product deep desulfuration.
The present invention uses the method for rare earth polyacid and ion liquid abstraction catalytic fuel oil oxidation sweetening, and its concrete steps are:
1, by 3.5-100mg rare earth polyacid, 0.01-1mL 20-30wt%H
2O
2, 0.5-1.5mL ionic liquid, 2-10mL oil fuel add in flask successively, 25-70 ℃ of stirring reaction 5-90min;
2, after having reacted, the upper oil phase clear liquid poured out is the oil fuel after deep desulfuration; Oil fuel remaining in flask is with after chloroform extraction, and what in flask, be left is rare earth polyacid, ionic liquid and water, removes in 5-10 hour and anhydrates by 70-100 ℃ of static oil bath evaporation, then adds 0.01-1mL 20-30wt%H
2O
2, 2-10mL oil fuel, by the condition of step 1, carry out the desulphurization reaction of next round;
3, repeat above-mentioned steps 2-15 time, realize rare earth polyacid and ionic liquid recycling.
Described rare earth polyacid is Na
9MW
10O
3632H
2O, M=Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
Described ionic liquid is that described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF
4), 1-butyl-3-Methylimidazole hexafluorophosphate ([BMIM] PF
6), 1-octyl group-3-methyl imidazolium tetrafluoroborate ([OMIM] BF
4) and 1-octyl group-3-Methylimidazole hexafluorophosphate ([OMIM] PF
6).
The invention has the advantages that: the present invention by catalyzed oxidation under the catalyst system of rare earth polyoxometallate, ionic liquid and hydrogen peroxide coupling, reaches the effect of deep desulfuration by the oil fuel of high sulfur-bearing at normal temperatures, realizes high-efficiency cleaning and the utilization of the energy.And catalyzer and ionic liquid are a kind of comparatively successful sulfur methods through circulating reaction repeatedly and do not degrade.In this catalyst system easily prepared by catalyzer, detection means is accurate, the reaction times is short, and the catalyzed oxidation transformation efficiency is high, and catalyzer is easy to be recycled.
The accompanying drawing explanation
Fig. 1 is the histogram of the sweetening effectiveness that obtains of the embodiment of the present invention 1 and embodiment 2.
The DBTO generated after circulation ten secondary responses in Fig. 2 embodiment 2
2With the DBT, the DBTO that buy
2Nuclear magnetic spectrum.
Embodiment
[embodiment 1]
1, the preparation of analog fuel oil:
The DBT that gets 1.4662g (7.793mmol, 98%) is dissolved in octane, and being mixed with the 250mL sulphur content is the analog fuel oil of 1000ppm.
2. catalytic oxidation desulfurization experiment:
By 26.5mg Na
9EuW
10O
3632H
2O, 0.05mL 30wt%H
2O
2, 1mL ionic liquid [BMIM] BF
4, 5mL analog fuel oil adds in 50mL twoport round-bottomed flask successively, under 30 ℃, carries out magnetic agitation reaction 0.5h; Wherein every 5min, get sample one time, each static rear taking-up supernatant liquid gas chromatographic analysis;
In analog fuel oil, the content of DBT is confirmed by reference to standard, analysis condition:
Injector temperature=340 ℃; Detector temperature=250 ℃; Furnace temperature=70 ℃; Carrier gas: High Purity Nitrogen; Sample size is 1 μ L.
3. catalyst recovery and circulation:
After having reacted, the upper oil phase clear liquid poured out is the oil fuel after deep desulfuration; Oil fuel remaining in flask is with after chloroform extraction, and what in flask, be left is rare earth polyacid, ionic liquid and water, removes in 8 hours and anhydrates by 80 ℃ of static oil baths evaporations, then adds 0.05mL 30wt%H
2O
2, 5mL analog fuel oil carries out the desulphurization reaction of next round.
[embodiment 2]
1. the preparation of analog fuel oil:
With embodiment 1.
2. catalytic oxidation desulfurization experiment:
By 10.61mg Na
9LaW
10O
3632H
2O, 0.03mL 30wt%H
2O
2, 1mL ionic liquid [BMIM] BF
4, 5mL analog fuel oil adds in 50mL twoport round-bottomed flask successively, under 30 ℃, carries out magnetic agitation reaction 0.6h; Wherein every 5min, get sample one time, each static rear taking-up supernatant liquid gas chromatographic analysis;
In analog fuel oil, the content of DBT is confirmed by reference to standard, analysis condition:
Injector temperature=340 ℃; Detector temperature=250 ℃; Furnace temperature=70 ℃; Carrier gas: High Purity Nitrogen; Sample size is 1 μ L.
3. catalyst recovery and circulation:
After having reacted, the upper oil phase clear liquid poured out is the oil fuel after deep desulfuration; Oil fuel remaining in flask is with after chloroform extraction, and what in flask, be left is rare earth polyacid, ionic liquid and water, removes in 6 hours and anhydrates by 90 ℃ of static oil baths evaporations, then adds 0.03mL 30wt%H
2O
2, 5mL analog fuel oil carries out the desulphurization reaction of next round;
4. repeating step 2 and 3,10 times, realize rare earth polyacid and ionic liquid recycling.
Claims (1)
1. the method for a rare earth polyacid and ion liquid abstraction catalytic fuel oil oxidation sweetening, is characterized in that, its concrete operation step is as follows:
1), by 3.5-100mg rare earth polyacid, 0.01-1mL20-30wt%H
2O
2, 0.5-1.5mL ionic liquid, 2-10mL oil fuel add in flask successively, 25-70 ℃ of stirring reaction 5-90min;
2), reacted after, the upper oil phase clear liquid poured out is the oil fuel after deep desulfuration; Oil fuel remaining in flask is with after chloroform extraction, and what in flask, be left is rare earth polyacid, ionic liquid and water, removes in 5-10 hour and anhydrates by 70-100 ℃ of static oil bath evaporation, then adds 0.01-1mL20-30wt%H
2O
2, 2-10mL oil fuel, by the condition of step 1), carry out the desulphurization reaction of next round; Reusable 2-15 time of rare earth polyacid and ionic liquid;
Described rare earth polyacid is Na
9MW
10O
3632H
2O, M=Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
Described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate, 1-octyl group-3-methyl imidazolium tetrafluoroborate and 1-octyl group-3-Methylimidazole hexafluorophosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100524807A CN102585888B (en) | 2012-03-02 | 2012-03-02 | Oxidative desulfurization method for rare earth polyacid and ionic liquid extraction catalysis fuel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100524807A CN102585888B (en) | 2012-03-02 | 2012-03-02 | Oxidative desulfurization method for rare earth polyacid and ionic liquid extraction catalysis fuel oil |
Publications (2)
| Publication Number | Publication Date |
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| CN102585888A CN102585888A (en) | 2012-07-18 |
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| US9127214B2 (en) | 2012-02-06 | 2015-09-08 | Shun-Sheng Cheng | Fuel desulfurization method |
| CN102863566B (en) * | 2012-09-28 | 2014-02-19 | 南开大学 | Application and preparation method for macroporous resin with polyoxometallate loaded by covalent bonds |
| CN104762101B (en) * | 2015-04-17 | 2017-01-25 | 北京化工大学 | Method for oxidative desulfurization of fuel oil by adopting polyacid intercalation trihydroxymethyl hydrotalcite and ionic liquid extraction catalysis |
| CN105061319A (en) * | 2015-08-11 | 2015-11-18 | 泉州理工职业学院 | Imidazole peroxy-molybdate and preparation method therefor |
| CN105802662B (en) * | 2016-05-16 | 2018-05-15 | 辽宁大学 | A kind of oxidation desulfurizing method using Janus base acidic catalysts |
| CN108636400B (en) * | 2018-04-28 | 2021-01-15 | 东北师范大学 | Hydrotalcite-based composite catalyst and preparation method and application thereof |
| CN108940379B (en) * | 2018-07-17 | 2020-12-08 | 东北师范大学 | Amphiphilic Lindqvist type polyacid TiO2Composite nanofiber and preparation method and application thereof |
| CN110124741A (en) * | 2019-06-18 | 2019-08-16 | 海南师范大学 | A kind of preparation method of the Hydroxyapatite-Supported heteropolyacid salt catalyst for catalytic oxidation desulfurization |
| CN112300831A (en) * | 2019-07-29 | 2021-02-02 | 中国石油大学(北京) | Method for removing sulfide in sulfur-containing raw oil by using ionic liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220293A (en) * | 2007-09-26 | 2008-07-16 | 江苏大学 | Method for ion liquid abstraction-catalytic oxidation desulfurization |
| CN101270299A (en) * | 2008-04-30 | 2008-09-24 | 武汉科技大学 | Method for oxidation sweetening of light-end products |
| CN102076410A (en) * | 2008-04-30 | 2011-05-25 | 康宁股份有限公司 | Catalysts on substrates and methods for providing the same |
-
2012
- 2012-03-02 CN CN2012100524807A patent/CN102585888B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220293A (en) * | 2007-09-26 | 2008-07-16 | 江苏大学 | Method for ion liquid abstraction-catalytic oxidation desulfurization |
| CN101270299A (en) * | 2008-04-30 | 2008-09-24 | 武汉科技大学 | Method for oxidation sweetening of light-end products |
| CN102076410A (en) * | 2008-04-30 | 2011-05-25 | 康宁股份有限公司 | Catalysts on substrates and methods for providing the same |
Non-Patent Citations (4)
| Title |
|---|
| 22-Isopolytungstate Fragment [H2W22O74]14-Coordinated to Lanthanide Ions;Amal H. Ismall;《Inorg.Chem.》;20091231;第48卷(第4期);第1559-1565页 * |
| Amal H. Ismall.22-Isopolytungstate Fragment [H2W22O74]14-Coordinated to Lanthanide Ions.《Inorg.Chem.》.2009,第48卷(第4期),第1559-1565页. |
| 周百斌.钼钨钒磷杂多酸稀土衍生物的合成、表征及催化性质.《中国稀土学报》.2001,第19卷(第5期),第393-397页. |
| 钼钨钒磷杂多酸稀土衍生物的合成、表征及催化性质;周百斌;《中国稀土学报》;20011031;第19卷(第5期);第393-397页 * |
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