CN105038841A - Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid - Google Patents
Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid Download PDFInfo
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- CN105038841A CN105038841A CN201510389950.2A CN201510389950A CN105038841A CN 105038841 A CN105038841 A CN 105038841A CN 201510389950 A CN201510389950 A CN 201510389950A CN 105038841 A CN105038841 A CN 105038841A
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- toluene
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 4
- 229920000570 polyether Polymers 0.000 title abstract description 4
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 29
- 230000023556 desulfurization Effects 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 8
- 125000005287 vanadyl group Chemical group 0.000 claims description 4
- 238000013316 zoning Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- 238000013019 agitation Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- -1 thioether sulfides Chemical class 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for catalyzing fuel oil O2 oxidation desulphurization The method adopting a polyether type oxovanadium heteropolyacid ionic liquid as a catalyst comprises the following steps: adding the catalyst, sulfur-containing fuel oil and a temperature control solvent toluene to an autoclave according to a molar ratio of the catalyst to the sulfide of 1:1.6-4.8 and a volume ratio of toluene to the fuel oil of 1:1.5-2.0, introducing oxygen to make pressure be 0.6-1.2MPa, and reacting at a temperature of 80-120DEG C for 0.5-2.5h. Compared with traditional methods, the method provided by the invention has the following advantages: 1, the catalyst simultaneously has two high-valence metals, so the oxidation catalysis ability is strong; 2, the catalyst has a temperature control chain, so a catalysis system has the characteristics of high-temperature homogeneous reaction and low-temperature separation of two phases, and also has the advantages of high homogeneous reaction catalytic activity, and easy separation of the catalyst and a product in a heterogeneous reaction; 3, the catalyst has stable performances, and the cycle use efficiency of the catalyst is high; and 4, the method is an environmentally friendly process route.
Description
Technical field
The present invention relates to environmental friendly catalysis field, specifically utilize a kind of method that polyether-type vanadyl heteropolyacid ionic liquid is catalyst fuel oil oxidation sweetening.
Background technology
The SOx that oil inflame gives off is one of important factor causing topsoil, and countries in the world have promulgated strict fuel oil sulfur-bearing standard in succession.At present, developed country performs Europe V standard just in succession, and namely sulphur content is lower than 10 μ g/g.Although China has also issued the state V standard identical with Europe V, at present still at execution state IV standards, namely sulphur content has been 50 μ g/g.Although current commercially available petrol and diesel oil is stripped of mercaptan, thioether sulfides wherein through Catalytic Hydrogenation Techniques, still containing thiophene, thionaphthene and dibenzothiophene class sulfide that micro-difficulty removes in oil product.Therefore, realize the target that China's petrol and diesel oil sulphur content reaches Europe V standard, key is to remove above-mentioned thiophene-type sulfide how efficiently.
In current existing non-hydrodesulfurization, the most potential desulfurization technology is catalytic oxidation desulfurization.Catalytic oxidation desulfurization technology is under the catalysis of catalyzer, utilize oxygenant by polarity for the sulfide-oxidation in oil product large sulfone, sulfoxide, recycling fuel oil and sulfone, feature that sulfoxide polarity gap is large, by extracting or adsorbing, isolate sulfone, sulfoxide, thus reach the object of desulfurization.Therefore, oxidation sweetening more easily removes in hydrogenating desulfurization, be difficult to removal thionaphthene and dibenzothiophene class sulfide.
In current existing catalytic oxidation desulfurization technology, with hydrogen peroxide (H
2o
2) technology the most ripe (Ind.Eng.Chem.Res., 2010,49,11760 of making oxygenant; Ind.Eng.Chem.Res., 2010,49,8998; Chem.Eur.J., 2012,18,4775; EnergyFuels, 2014,28,2754; CN104689850A; CN104312621A; CN103666536A; CN103333711A).Due to O
2or air is that oxygenant can overcome H
2o
2be heated and the intrinsic shortcoming such as easily decompose, be considered to a kind of rising eco-friendly fuel desulfuration technology.But, with O
2or air is oxygenant, its oxidation activity comparatively H
2o
2relatively low, need to carry out under the catalysis of catalyzer, sometimes also need the existence of co-oxidation sacrifice agent aldehyde.The O of catalysis
2oxidation sweetening has document and patent report (Fuelprocessingtechnology, 2009,90,317; EnergyFuels, 2004,18,116; CatalToday, 2007,123,276; CN103834432A).Heteropllyacids compound containing high-valence state transition metal is used as oxide catalyst, and arouse widespread concern, it is for catalytic oxidation desulfurization, shows good catalytic effect (GreenChem., 2010,12,1954; Chem.Commun., 2012,48,11647; Chem.Commun.2007,2,150; Catalysis journal, 2014,35,1433).But current Problems existing: one is that the catalytic activity of catalyzer need further raising, to realize the oxidizable object removed completely of thiophene-type sulfide in fuel oil; Two be catalyzer recycle weak effect.The reason that catalyst activity is low: one is because the catalyzed oxidation ability of catalyzer itself is low; Two is because current oxidation sweetening system still belongs to solid-liquid or liquid-liquid two-phase system, catalyzer with reaction substrate contact area is little, mass transfer diffusional resistance greatly, cause speed of reaction slow.
Ionic liquid has that structure can design, character controllable, advantages of environment protection, utilizes its structure designability, catalytic active center can be assembled in ionic liquid structure, make it while having catalytic activity, guarantee reusing of ionic liquid.But constructed reaction system majority is biphasic catalysis, speed of response is obviously not as homogeneous catalysis.Therefore, the ideal response system that ionic liquid participates in should be, during pyroreaction, ionic liquid and reactant coexist a phase, reaction terminates rear ionic liquid and product office two-phase again, reach the object of " high temperature homogeneous reaction; low temperature two-phase laminated flow ", the recovery of realization response-isolation integral and ionic liquid and reusing.
Summary of the invention
In order to solve, the catalyst activity existed in existing desulfurization technology is low, the dysoxidizable problem of thiophene-type sulfide, the present invention proposes a kind of method that polyether-type vanadium oxa-polyacid ionic liquid is catalyst fuel oil oxidation sweetening.The method technique is simple, and catalyst activity is high, it is effective to recycle, for deep desulfurization of fuel oil provides an eco-friendly operational path.
The present invention utilizes the designability of ionic liquid structure, structure of controlling temperature unit (polyether chain) is incorporated in the cationic structural of ionic liquid, in the positively charged ion that high-valence state vanadium atom is incorporated into ionic liquid or anion structure, and the heteropolyacid root be made up of high-valence state tungsten is designed to the negatively charged ion of ionic liquid, formulate out new class and there is catalyzed oxidation and the bifunctional ionic-liquid catalyst of temperature control, for the O of catalysis fuel oil
2oxidation sweetening.The feature of this catalyzer is: (1) has vanadium and tungsten two kinds of catalytic oxidation activity centers simultaneously, gives the catalytic activity that catalyzer is higher; (2) there is unique temperature-control performance, give the feature that catalytic desulfurization system has " high temperature homogeneous reaction; low temperature two-phase laminated flow ", during high temperature, catalyzer can carry out with the oxidation desulfur reaction of sulphur-containing burning oil in a phase, and reaction terminates automatically to be separated into two-phase again to catalyzer during room temperature and fuel oil.Therefore, new desulfurization system can solve low, the dysoxidizable problem of thiophene-type sulfide of catalytic activity that current oxidation sweetening catalyst system exists effectively, reaches the object of deep desulfurization of fuel oil.
Technical scheme of the present invention is:
In autoclave, add a certain amount of catalyzer, sulphur-containing burning oil and temperature control solvent toluene, with the air several in replacement of oxygen still, be then filled with the oxygen of certain pressure, heat and open magnetic agitation, reacting certain hour at a certain temperature.After reaction terminates, be cooled to room temperature, release, drive still.Catalyzer phase and the layering of oil product phase, the oil product on upper strata, with after isopyknic DMF (DMF) extraction, measures desulfurization degree; The catalyzer of lower floor without the need to process, direct reuse.
Described catalyzer is the stearylamine base vanadyl heteropolyacid ionic liquid containing polyether chain, is [AC
18]
4(VO) (PW
12o
40)
2, [AC
18]
4(VO
3) (PW
12o
40), [AC
18]
6(VO
3)
3(PW
12o
40) one wherein, wherein AC
18structural formula as follows:
The mol ratio of catalyzer of the present invention and oil product sulphur content is generally 1:1.6 ~ 4.8, the volume ratio of toluene and oil product is generally 1:1.5 ~ 2.0, oxygen pressure is generally 0.6 ~ 1.2MPa, and temperature of reaction is generally 80 ~ 120 DEG C, and the reaction times is generally 0.5 ~ 2.5h.
The present invention compares existing fuel catalytic oxidative desulfurization techniques, and tool has the following advantages:
1, catalyzer has vanadium and tungsten two kinds of high-valence state metals simultaneously, and catalyzed oxidation ability is strong.
2, catalyzer has temperature control chain, gives catalyst system and has the feature of " high temperature homogeneous reaction, low temperature two-phase laminated flow ", maintains that homogeneous reaction catalytic activity is high, heterogeneous reaction catalyzer and the segregative advantage of product simultaneously.
3, catalyst performance stabilised, recycles efficiency high.After recycling 22 times, desulfurization degree is still more than 90%.
4, take ionic liquid as catalyzer, O
2for oxygenant, belong to environmentally friendly technology route.
Specific implementation method
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
In following examples, fuel oil used is the analog gasoline a certain amount of thionaphthene being dissolved in octane and being made into, and recording its sulphur content with WK-2D type Microcoulomb instrument is 667.972mgL
-1.
Embodiment 1: with [AC
18]
4(VO
3) PW
12o
40for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:1.6, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.0MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 1.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 96.0%.
Embodiment 2: with [AC
18]
6(VO
3)
3pW
12o
40for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:1.6, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.0MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 1.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 96.2%.
Embodiment 3: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:3.2, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 0.6MPa, heat and open magnetic agitation, at temperature 80 DEG C, react 1 hour.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 94.0%.
Embodiment 4: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:4.8, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.0MPa, heat and open magnetic agitation, at temperature 80 DEG C, react 2 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 95.0%.
Embodiment 5: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:4.8, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 0.6MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 1.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 97.2%.
Embodiment 6: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:2.4, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.0MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 2.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 98.8%.
Embodiment 7: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:3.2, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.2MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 0.5 hour.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 97.0%.
Embodiment 8: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:2.4, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 0.6MPa, heat and open magnetic agitation, at temperature 120 DEG C, react 2 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 96.1%.
Embodiment 9: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:3.2, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 0.8MPa, heat and open magnetic agitation, at temperature 120 DEG C, react 2.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 97.9%.
Embodiment 10: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:4.8, volume ratio V (toluene): V (fuel oil)=1:2.0 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.2MPa, heat and open magnetic agitation, at temperature 120 DEG C, react 1 hour.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 96.6%.
Embodiment 11: with [AC
18]
4(VO) (PW
12o
40)
2for catalyzer, the ratio of n (catalyzer): n (sulfide)=1:1.6, volume ratio V (toluene): V (fuel oil)=1:1.5 in molar ratio, take catalyzer, fuel oil and toluene, add in reactor simultaneously.With the air several in replacement of oxygen still, be then filled with the oxygen of 1.0MPa, heat and open magnetic agitation, at temperature 100 DEG C, react 1.5 hours.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of fuel oil phase.Reclaim upper strata fuel oil phase, after isopyknic DMF extraction, measuring desulfurization degree is 95.1%.
Embodiment 12-33:
Catalyzer, with embodiment 6, is just changed into the catalyzer reclaimed in embodiment 6 by experiment condition and step, carries out repeating reuse experiment for 22 times, and finally measuring desulfurization degree is 90.3%.
Claims (2)
1. a catalysis fuel oil O
2the method of oxidation sweetening, it is characterized in that with polyether-type vanadyl heteropolyacid ionic liquid for catalyzer, n (catalyzer): n (sulfide)=1:1.6 ~ 4.8 in molar ratio, the ratio of volume ratio V (toluene): V (fuel oil)=1:1.5 ~ 2.0, catalyzer is added in autoclave, sulphur-containing burning oil and toluene, then the oxygen of 0.6 ~ 1.2MPa is filled with, at temperature 80 ~ 120 DEG C, react 0.5 ~ 2.5 hour, after reaction terminates, be cooled to room temperature, catalyzer phase and fuel oil phase AUTOMATIC ZONING, the fuel oil on upper strata is with after isopyknic DMF extraction, measure desulfurization degree, the catalyzer of lower floor is without the need to process, direct reuse.
2. in accordance with the method for claim 1, catalyzer is [AC
18]
4(VO) (PW
12o
40)
2, [AC
18]
4(VO
3) (PW
12o
40), [AC
18]
6(VO
3)
3(PW
12o
40) one wherein, wherein AC
18structural formula as follows:
m＝a+b(125～158)
R＝n-C
4H
9，n-C
8H
15，n-C
16H
31。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866281A (en) * | 2016-09-28 | 2018-04-03 | 中国科学院宁波材料技术与工程研究所 | Hydroxy functionalized heteropolyacid catalyst, its preparation method and application |
| CN110354908A (en) * | 2019-07-16 | 2019-10-22 | 闽江学院 | Polyether-based is functionalized vanadium doping heteropoly acid poly ion liquid, synthetic method and its is preparing the application on hexamethylene lactone |
| CN113754875A (en) * | 2021-10-08 | 2021-12-07 | 山东科技大学 | Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof |
-
2015
- 2015-07-05 CN CN201510389950.2A patent/CN105038841A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866281A (en) * | 2016-09-28 | 2018-04-03 | 中国科学院宁波材料技术与工程研究所 | Hydroxy functionalized heteropolyacid catalyst, its preparation method and application |
| CN110354908A (en) * | 2019-07-16 | 2019-10-22 | 闽江学院 | Polyether-based is functionalized vanadium doping heteropoly acid poly ion liquid, synthetic method and its is preparing the application on hexamethylene lactone |
| CN110354908B (en) * | 2019-07-16 | 2022-06-07 | 闽江学院 | Polyether-based functionalized vanadium-doped heteropoly acid polyion liquid, synthesis method and application thereof in preparation of cyclohexadene |
| CN113754875A (en) * | 2021-10-08 | 2021-12-07 | 山东科技大学 | Polyether type heteropoly acid temperature control ionic liquid for removing basic nitrides of gasoline and diesel oil and preparation method thereof |
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