CN109908962A - The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application - Google Patents
The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application Download PDFInfo
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- CN109908962A CN109908962A CN201910159108.8A CN201910159108A CN109908962A CN 109908962 A CN109908962 A CN 109908962A CN 201910159108 A CN201910159108 A CN 201910159108A CN 109908962 A CN109908962 A CN 109908962A
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- ionic liquid
- heteropoly acid
- amination
- magnetic composite
- type structure
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 100
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 97
- 238000005576 amination reaction Methods 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 240000008866 Ziziphus nummularia Species 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 38
- 241001247821 Ziziphus Species 0.000 claims abstract description 36
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000000696 magnetic material Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 14
- 238000004088 simulation Methods 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 150000008282 halocarbons Chemical class 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 241000238370 Sepia Species 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BANOTGHIHYMTDL-UHFFFAOYSA-N 2-bromo-1-methylimidazole Chemical compound CN1C=CN=C1Br BANOTGHIHYMTDL-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- -1 cyclopentadiene carbonyl molybdenum Chemical compound 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 229910017135 Fe—O Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003196 chaotropic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a kind of ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, preparation method and application, it includes heteropoly acid ionic liquid and amination magnetic composite that the composite material, which prepares raw material, by ultrasonic immersing method that heteropoly acid is ionic liquid loaded in obtaining composite material on amination nano magnetic material.Preparation step are as follows: substitution reaction is first respectively adopted and prepares heteropoly acid ionic liquid, solvent-thermal method preparation amination magnetic composite, then the ionic liquid loaded amination magnetic composite of heteropoly acid is prepared using ultrasonic carrying method.The product that the method for the present invention obtains is in powdered, sepia, and even particle size distribution has jujube cake type structure, and property is stablized.It overcomes magnetic material and is easy the shortcomings that reuniting, resulting materials good dispersion, magnetic property are high, raw material is easy to get, yield is high；Magnetic and catalytic activity is had both, can be effectively used for the catalyst of oil sample desulfurization, the separable recycling of catalyst.
Description
Technical field
The present invention relates to a kind of ionic liquid loaded amination magnetic composites of jujube cake type structure heteropoly acid, preparation method
And its application technology, specially heteropoly acid ionic liquid and amination magnetic composite preparation method and its jujube cake type structure are miscellaneous
The preparation method of the ionic liquid loaded amination magnetic composite of polyacid, and using jujube cake type structure heteropoly acid of the present invention from
For sub- fluid load amination magnetic composite as catalyst, hydrogen peroxide is the desulfurization of oxidizer catalytic oil sample, realizes stone
The purpose of deep desulfuration of oiling work.
Background technique
With advances in technology with development, petroleum push process of industrialization in play an important role.But with sulphur in petroleum
Changing sulphur existing for the forms such as hydrogen, thiophene, disulphide not only influences oil quality, and burn the oxysulfide (SO generatedx) more
It is that great threat is generated to ecological environment and human health.Therefore how efficient deep desulfuration obtain the petroleum of ultra-low sulfur at
For the hot spot of the research of petrochemical industry instantly.
The means of currently used deep desulfuration include hydrodesulfurization and non-hydrodesulfurization.Traditional hydrodesulfurization means are deposited
It is being difficult to remove the drawbacks such as thiophene substance, cost are excessively high, condition is harsh, time-consuming and energy consumption is high.Such as: Ye (Journal of
Hazardous Materials, 2019,366:432-438) Hydrobon catalyst, but catalyst have been synthesized by microwave method
Preparation needs completed at a high temperature of 700 DEG C.Rather than hydrodesulfurization due to its low energy consumption, environmentally protective increasingly by scientific research
The favor of personnel.Non-hydrodesulfurization includes that absorption desulfurization is (such as: Zheng (Journal of Hazardous
Materials, 2019,362:424-435) utilize B2O3The Ag-CeO of modificationx/TiO2-SiO2Composite material can effectively inhale
4,6- dimethyl Dibenzothiophene in attached simulation oil sample, thus realize absorption desulfurization), abstraction desulfurization (such as: Juliao
(Applied Catalysis B:Environmental, 2018,230:177-183) is with cyclopentadiene carbonyl molybdenum match
CpMo(CO)3R is catalyst, and hydrogen peroxide is oxidant, and the oxidation sweetening of a variety of thiophene is realized by ion liquid abstraction), it is raw
(such as: Cano (Journal of Cleaner Production, 2018,181:663-674) uses anaerobic organism for object desulfurization
Technology desulfurization) and oxidation sweetening (such as: Pouladi (J Journal of Cleaner Production, 2019,209:
The experiment condition of oxidation sweetening 965-977) is optimized by Response surface meth od) etc..Wherein oxidation sweetening is such as double by oxidant
Oxygen water (H2O2) etc., organic sulfur compound is oxidized to corresponding sulfone or sulfoxide, improves dissolution of the organic sulfur compound in polar solvent
Degree, by means and the separated from petroleum such as extracting, distilling, to achieve the purpose that deep desulfuration.
In recent years, ionic liquid is referred to as " green solvent ", because it is with good thermal stability and due to chemical stability
It is widely used in catalytic oxidation desulfurization.Ionic liquid is introduced into in oxidation-reduction quality heteropoly acid, dual oxide can be formed
The heteropllyacids ionic liquid in activated centre, and show excellent catalytic activity.Such as Xun (Chemical
Engineering Journal, 2016,288:608-617) it has been synthesized by sol-gel method with high catalytic activity
(SiW12O40- IL) heteropoly acid ionic-liquid catalyst, the catalyst is at 60 DEG C, the ratio of the amount of the substance of oxidant and sulphur: n (O/
When S)=4, desulfurization degree reaches 99.9%, and it is good desulphurizing activated to illustrate that heteropoly acid ionic liquid has.But heteropoly acid ionic liquid
There is also the drawbacks such as the rate of recovery is low for body, therefore suitable solid support method is selected to be particularly important.Common carrier has SiO2、
Al2O3、Fe3O4Deng wherein Fe3O4With stronger magnetism, the quick separating of catalyst and oil sample can be realized, increasingly become heat
One of the carrier of door.If heteropoly acid ionic liquid and magnetic material can be combined to obtain the ionic liquid loaded magnetic coupling of heteropoly acid
Material, it is expected to the advantages that realizing its highly selective, good dispersion and being used repeatedly, undoubtedly catalyst regeneration with return
Receiving utilize, improve oil quality etc. has important and positive meaning.
Summary of the invention
The present invention be directed to the prior art above-mentioned deficiency, provide it is a kind of selectivity height, good dispersion, can be used repeatedly
The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid.
In order to solve the above-mentioned technical problem, a kind of the technical solution adopted by the present invention are as follows: jujube cake type structure heteropoly acid ion
Fluid load amination magnetic composite, it includes that heteropoly acid ionic liquid and amination magnetism are multiple which, which prepares raw material,
Condensation material is ionic liquid loaded miscellaneous more in finally obtaining on amination nano magnetic material by heteropoly acid by ultrasonic immersing method
Acid ion fluid load amino nano magnetic composite materials.
The above-mentioned ionic liquid loaded amination magnetic composite preparation method of jujube cake type structure heteropoly acid of the present invention, step
It suddenly include: to prepare heteropoly acid ionic liquid by using substitution reaction, amination magnetic composite is prepared using solvent-thermal method,
It is by ultrasonic immersing method that heteropoly acid is ionic liquid loaded on amination nano magnetic material again, finally obtain heteropoly acid ion
Fluid load amino nano magnetic composite materials.
The present invention is above-mentioned to prepare heteropoly acid ionic liquid, specifically are as follows: add N- methylimidazole or pyridine in magnetic agitation
Halogenated hydrocarbons is slowly added dropwise when heat reflux, after being added dropwise, continues return stirring to complete reaction；It cools down after completion of the reaction, uses second
Acetoacetic ester repeatedly extracts excessive response raw material, and vacuum distillation removes remaining ethyl acetate, obtains ionic liquid；Further stirring
It mixes down and phosphotungstic acid aqueous solution is slowly added dropwise, continue to flow back after being added dropwise, be evaporated under reduced pressure after reaction, remove in reaction solution
Extra moisture and by-product is dried to get heteropoly acid ionic liquid is arrived.
Above-mentioned halogenated hydrocarbons is one of chloro or bromo-hydrocarbons of C4~C12；
The mass ratio of the material of above-mentioned N- methylimidazole or pyridine and halogenated hydrocarbons is 0.5:1~1:5, preferably 1:1~1:
2；The return stirring reaction temperature of N- methylimidazole or pyridine and halogenated hydrocarbons be 60~150 DEG C, the reaction time be 2~for 24 hours, preferably
Reaction temperature be 80~100 DEG C, the reaction time be 6~10h；Phosphotungstic acid aqueous solution is saturated solution；Ionic liquid and phosphorus tungsten
The mass ratio of the material of acid is 2:1~8:1, and the mass ratio of the material of preferred ionic liquid and phosphotungstic acid is 3:1~5:1；It drips
Continuing return time after finishing is 2-12h, and continuing return time after being preferably added dropwise is 6-10h；Drying temperature be 60-120 DEG C,
Time is 2~for 24 hours, preferred drying temperature is preferably 80-100 DEG C, the time is 6~10h.
Why the present invention selects N- methylimidazole or pyridyl group ionic liquid, can by adjust substituent group type come
The structure and performance of controlled material, such as dissolubility, polarity, so as to obtain for the selection of different types of sour product not
Same degradation catalyst.
The above-mentioned preparation amination magnetic composite of the present invention, specifically are as follows: ferric iron and acetate are dissolved in ethylene glycol
In；The mass ratio of ferric iron and acetate be 1:1~1:10, mass concentration of the ferric iron in ethylene glycol be 20~400g/L,
Mass concentration of the acetate in ethylene glycol is 40~600g/L；5~30min is stirred at room temperature；Then organic polyamine is added
5-80mL, stirring is to forming stable orange solution；Reaction solution is transferred in reaction kettle, 100~240 DEG C of reactions 2~
24h；It is 7 that Magneto separate, which is washed to pH value, after cooling, is dried in vacuo up to amination magnetic composite.
Above-mentioned ferric iron is one of ferric trichloride, ferric sulfate.
Above-mentioned acetate is one of sodium acetate or ammonium acetate.
Mass concentration of the above-mentioned ferric iron in ethylene glycol is preferably 40~120g/L.
Mass concentration of the above-mentioned acetate in ethylene glycol is preferably 60~180g/L.
Above-mentioned organic polyamine is ethylenediamine, Diethylenetriamine, three second tetramines, a kind of in tetren.
The dosage of above-mentioned organic polyamine is preferably 20~60mL.
Reaction temperature in above-mentioned reaction kettle is preferably 150~200 DEG C, reaction time preferably 10~20h.
The present invention is above-mentioned to prepare the ionic liquid loaded amination composite material of heteropoly acid, specifically are as follows: respectively will be above-mentioned
For amination magnetic composite ultrasonic disperse into aqueous solution, making its mass concentration is preferably 5~100g/L, it is above-mentioned prepare it is miscellaneous more
Acid ion liquid is dissolved in acetone, and making its mass concentration is preferably 20~500g/L, is slowly added dropwise to amination magnetic coupling
Material ultrasonic disperse into aqueous solution so that the mass ratio of amination magnetic composite and heteropoly acid ionic liquid be 1:1~
1:10；Continue 5~30min of ultrasound after being added dropwise；After reaction, be dried in vacuo at 30~100 DEG C 2~24 hours to get
To the ionic liquid loaded amination composite material of heteropoly acid.
The mass concentration of above-mentioned amination magnetic composite in water is preferably 10~40g/L.
The mass concentration of above-mentioned heteropoly acid ionic liquid in acetone is preferably 50~150g/L.
The mass ratio of above-mentioned amination magnetic composite and heteropoly acid ionic liquid is preferably 1:4~1:6.
It is catalyst the present invention also provides a kind of ionic liquid loaded amination composite material of heteropoly acid, hydrogen peroxide is oxidation
The application of agent catalysis oil sample desulfurization.
According to the present invention preferably, the application of the ionic liquid loaded amination composite material of heteropoly acid, for being catalyzed stone
Oil samples desulfurization.
The specific catalytic sweetening method of the present invention is as follows:
Under the conditions of shaken at room temperature, it is multiple to put into the jujube ionic liquid loaded amination magnetism of cake type structure heteropoly acid of the invention
Condensation material, dosage be every rising mould intend the ionic liquid loaded amination magnetic composite dosage of heteropoly acid in oil sample be 0.2~
5g, ultrasound keep its evenly dispersed, rapidly join H2O20.04-10mL of solution (30wt%), ultrasonic certain time (2-20min)
Afterwards, separating catalyst and simulation oil sample under external magnetic fields, take 5mL acetonitrile extraction.Under the conditions of 305-345K, oscillation speed
Rate is 100~300 revs/min, and the time is 30~180 minutes；Desulfurization degree can be greater than 85%.
The advantages of the present invention:
1. the present invention is first respectively adopted, substitution reaction prepares heteropoly acid ionic liquid, solvent-thermal method preparation amination magnetism is answered
Condensation material, then the ionic liquid loaded amination magnetic composite of heteropoly acid is prepared using ultrasonic carrying method, it is found through characterization
The available magnetic composite with special jujube cake type structure of this technology of preparing efficiently solves magnetic material appearance
Problem easy to reunite.Experiments have shown that: the invention operating procedure is simple, low in cost, obtained composite material even particle size distribution,
Property is stablized, and rapid reaction, raw material are easy to get, yield is high, can be effectively used for the catalyst of oil sample desulfurization, realizes material
Catalysis and magnetic double function, are conducive to the separation and recovery of catalyst.
2. of the invention has both catalysis and magnetic double function, and has special jujube cake type structure heteropoly acid ionic liquid
Amination magnetic composite is loaded, the cost of material of use is low to be easily obtained, and is easy purifying, and have to oil sample desulfurization
High catalytic activity；The present invention has preparation method simple, low in cost, and resulting materials are cheap and easy to get, environmental-friendly, Ke Yishi
The purpose of existing environmental protection and resource high added value.
3. the present invention unconventional silica using the amido modified ferroso-ferric oxide of direct one-step synthesis method
Four iron oxide magnetic cores of modification, the advantage of this method are mainly reflected in: (1) magnetic core content is high, can make Magneto separate effect
It is good；(2) there is amino functional modification on ferroso-ferric oxide surface, is conducive to further be firmly combined with heteropoly acid ionic liquid, no
The stability for improving only material improves the dispersibility of material, improve the specific surface area of material and also form it is special
Jujube cake type structure；In addition, chemical synthesis of the invention can carry out in homogeneous system, reaction uniformly, is easy to control, gained
Material particle size is uniform.
4. jujube cake type structure of the invention can be observed that by Electronic Speculum, it is specifically shown in attached drawing 4；It is this special
The advantage of structure is: (1) a large amount of heteropoly acid ionic liquids are densely embedded in amination magnetic material surface, illustrate to pass through leaching
Stain method carried heteropoly acid ionic liquid is more readily dispersed in amination magnetic material surface, is not susceptible to agglomeration；(2) jujube cake type
The stability of material can be improved in structure, improves the dispersibility of material, improves the specific surface area of material, it is anti-to be conducive to catalytic desulfurization
The generation answered.
5. reaction condition of the present invention is mild, cost of material is cheap, easy to operate, at low cost, and used is that catalysis oxidation is de-
Sulphur technique, can more thoroughly desulfurization, be not present secondary pollution problems；Resulting materials collection amino functional magnetic of the present invention
Core, ionic liquid and heteropoly acid are them with the active important leverage of high catalytic desulfurization in one.
Detailed description of the invention
Fig. 1 is that the ionic liquid loaded amination magnetic composite preparation flow of jujube cake type structure heteropoly acid of the invention shows
It is intended to.
Fig. 2 is the ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid according to embodiments of the present invention
Infrared spectrogram (FTIR).
Fig. 3 is the embodiment of the present invention, the obtained ionic liquid loaded amination magnetic coupling material of jujube cake type structure heteropoly acid
The X-ray diffracting spectrum (XRD) of material.
Fig. 4 is that according to embodiments of the present invention, the obtained jujube ionic liquid loaded amination magnetism of cake type structure heteropoly acid is multiple
The transmission electron microscope (TEM a) and (SEM b) photo of condensation material.
Fig. 5 is the embodiment of the present invention, the obtained ionic liquid loaded amination magnetic coupling material of jujube cake type structure heteropoly acid
The X-ray power spectrum (XPS) (a-f) of material.
Specific embodiment
With reference to the accompanying drawing and specific embodiment is described further the contents of the present invention, makes the purpose of the present invention and effect
Fruit is more obvious, but the present invention is not limited solely to following embodiment.Preparation technology flow chart of the present invention is as shown in Figure 1, specific
Step is referring to each embodiment.
Embodiment 1
It takes 0.1mol N- methylimidazole heating water bath and 0.1mol is slowly added dropwise when temperature reaches 80 DEG C in magnetic agitation
Bromination of n-butane.After being added dropwise, temperature is controlled at 85 DEG C and is stirred to complete reaction, is obtained golden yellow, transparent, thick
Liquid.It is cooled to 50 DEG C after completion of the reaction, excessive response raw material is repeatedly extracted with ethyl acetate, vacuum distillation removes remaining second
Acetoacetic ester obtains bromo N- methylimidazole ionic liquid.
Gained bromo N- methylimidazole ionic liquid further acts on obtaining heteropoly acid ionic liquid with phosphotungstic acid: measuring
12mmol bromo N- methylimidazole ionic liquid, weighs 3mmol phosphotungstic acid and is allowed to be dissolved completely in deionized water, while stirring
Salkowski's solution is slowly added dropwise, gradually appears white precipitate.Flow back at 60 DEG C 8h after being added dropwise.Decompression is steamed after reaction
It evaporates, removes moisture and HBr extra in reaction solution, dry 12h at 80 DEG C obtains heteropoly acid ionic liquid.
Amination Fe is obtained using solvent-thermal method3O4: 4g FeCl is weighed respectively3·6H2O and 12g anhydrous sodium acetate is dissolved in
In 120mL ethylene glycol, 10min is stirred at room temperature.Then 40mL ethylenediamine is added, stirring is to forming stable orange solution.
Reaction solution is transferred in reaction kettle, reacts 8h at 180 DEG C, with magnet collects black product after cooling, with deionized water and
Dehydrated alcohol washing is several times 7,80 DEG C of vacuum drying 12h to get amination Fe to pH value3O4。
Finally by the ionic liquid loaded amino-magnetic composite material of ultrasonic immersing method heteropoly acid: taking 0.1g amination
Fe3O4, 10mL deionized water is added, ultrasound makes it be uniformly dispersed.By 0.5g heteropoly acid ion liquid dissolving in 10mL acetone,
It is slowly added dropwise in ultrasound into amination Fe3O4In, make heteropoly acid ionic liquid and amination Fe3O4The amino on surface is sufficiently made
With sufficiently to load.Continue ultrasound 10min after being added dropwise.After ultrasound, 80 DEG C of vacuum drying 12h remove excessive third
Ketone finally obtains the ionic liquid loaded amino-magnetic composite material of heteropoly acid.
The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid of the present embodiment, with bromo N- methyl
Imidazol ion liquid is raw material, specific synthesis path are as follows:
The operating procedure of embodiment 2~6 is shown in Table 1 institute with embodiment 1, raw material, composition of raw materials and preparation condition parameter
Show.
1 embodiment of the present invention of table, 1~6 raw material components and preparation parameter
The ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid prepared by the embodiment of the present invention is led to
Cross infrared spectrogram (FTIR), X-ray diffracting spectrum (XRD), transmission electron microscope (TEM) photo, scanning electron microscope (SEM) photo and
The means such as X-ray power spectrum (XPS) characterize it, and the catalytic oxidation desulfurization of simulation oil sample is applied to using it as catalyst.
Fig. 2~Fig. 5 is the according to embodiments of the present invention 1 obtained ionic liquid loaded amino of jujube cake type structure heteropoly acid respectively
Change infrared spectrogram (FTIR), the X-ray diffracting spectrum (XRD), transmission electron microscope (TEM) photo, scanning electricity of magnetic composite
Mirror (SEM) photo and X-ray power spectrum (XPS).
By Fig. 2 (a) it is found that 1640cm-1For the characteristic absorption peak of N-H, 582cm-1For Fe3O4Fe-O key characteristic absorption
Peak.Fig. 2 (b) has the characteristic absorption peak of 4 typical Keggin-type heteropolyanions, and ownership is center tetrahedron (P-respectively
O): 1080cm-1, (W=O): 978cm-1, 891cm-1And 802cm-1Place respectively corresponds WO6Corner-sharing in octahedral structure is octahedra
Between bridged bond (W-Oc- W) and (W-Ob—W)。1570cm-1For the stretching vibration peak of the skeleton C=N of imidazole ring, 1470cm-1
And 1380cm-1For the C-H flexural vibrations peak in pendant methyl, 1160cm-1For C-H flexural vibrations peak on imidazole ring.Fig. 2 (c),
That is: remained in the ionic liquid loaded amino-magnetic composite material of heteropoly acid heteropoly acid structure with Keggin and ionic liquid and
The principal character peak of amination magnetic core.
From figure 3, it can be seen that 2 angles θ, which are located at 6.82 °, 8.62 °, 9.62 °, 10.60 °, there is the feature diffraction of heteropoly acid
Peak (JCPDS 70-0705) is respectively belonging to (010), (200), (002) and (102) crystal face, in FI-IR characterization
Keggin-type heteropolyanion is consistent.2 angles θ of amination magnetic core are located at 30.35 °, 36.41 °, 40.97 °, 57.20 °, 59.45 °
Characteristic diffraction peak and orthorhombic crystalline structure standard spectrogram (JCPDS 76-0957) it is almost the same, be respectively belonging to (220),
(311), (422), (511) and (446) crystal face.There is more new diffraction maximum between 15-35 °, thus it is speculated that may be ionic liquid
It influences.
Scheme from the TEM and SEM of Fig. 4 sample.From Fig. 4 (a) it can be seen that the heteropoly acid loaded by infusion process from
Sub- fluid load amino-magnetic composite material is in relatively regular spherical structure, and average grain diameter is in 50-100nm or so；And heteropoly acid from
Sub- liquid can be well dispersed in amination magnetic material gap., it is apparent that a large amount of heteropoly acids from Fig. 4 (b)
Ionic liquid is densely embedded in amination magnetic material surface, illustrates to be easier to by infusion process carried heteropoly acid ionic liquid point
It dissipates and forms " jujube cake type structure " in amination magnetic material surface, be not susceptible to agglomeration.
Find out from the XPS map of Fig. 5 sample, which is made of this six kinds of elements of Fe, O, N, P, W, C (from Fig. 5
(a)), wherein the two characteristic peaks of 710.99 and 401.62eV are respectively belonging to the Fe of Fe2p3O4With the imidazole ring of N1s, show miscellaneous
Polyacid ionic liquid is successfully incorporated on amination magnetic material.Fig. 5 (b) shows that wider overlapped signal occurs in C1s,
Peak-fit processing is done to it and is divided into four characteristic peaks, in conjunction with that can be respectively 284.67,285.39,286.72 and 289.20eV, be said
It is bright that there are C=C, C-O, C-S and C=N key forms.Shown in W4f such as Fig. 5 (c), occur apparent bicharacteristic peak in figure,
Its combination can be respectively 36.23 and 38.37eV, respectively correspond W4f7/2(- WN) and W4f5/2(—WO3) spin(-)orbit, show W
With W6+Form exist.Compared with the W4f of simple heteropoly acid, W4f7/2Combination can be moved to 36.23eV by 34eV, 37eV is moved
Move to 38.37eV, this may be because heteropoly acid chaotropic body rear W=O key in conjunction with amination magnetic material be converted into it is weaker
W-O-Fe key.The combination of N1s can be moved to 401.62eV from 399eV in Fig. 5 (d), illustrate heteropoly acid chaotropic body and amination
Magnetic material surface amino groups are coordinated.There are two characteristic peaks in Fe2p in Fig. 5 (e), and corresponding combination can be 710.99
And 723.54eV, thus it is speculated that be likely to form Fe-O-C.Occur a broad peak in Fig. 5 (f), occurs three after doing peak-fit processing
A characteristic peak, corresponding combination can be respectively 529.90 (Fe-O), 531.24 (- OH) and 533.69eV (C-O).Above-mentioned knot
Fruit shows that heteropoly acid ionic liquid successfully loads on amination magnetic material, and still retains heteropoly acid ionic liquid
Structure with Keggin.By calculating peak area it is found that the mass percent of Fe, W, N are respectively 2.90%, 18.55% and 2.94%.
Here is the catalytic oxidation desulfurization application examples of 1 pair of embodiment simulation oil sample.
Application examples 1:
The 1 gained jujube ionic liquid loaded amination magnetic composite of cake type structure heteropoly acid of embodiment is applied to simulation
The catalytic oxidation desulfurization of oil sample.Using dibenzothiophenes as sulphur source, normal octane is simulation oil sample, prepares a series of concentration (100-
Simulation oil sample 2000mg/g) takes 50mL to simulate oil sample, is separately added into the heteropoly acid ion of certain mass (0.005-0.025g)
Fluid load amino-magnetic composite material, ultrasound keep its evenly dispersed, rapidly join H2O2Solution (30wt%) (4.00-12.00 μ
L), under the conditions of 305-345K, after ultrasonic certain time (2-20min), separating catalyst and simulation under external magnetic fields
Oil sample takes 5mL acetonitrile extraction.KB-5 capillary column 30m × 0.32mm × 0.50 μ (is equipped with using PERSEE G5 gas chromatograph
M) and flame ionization detector analysis normal octane in dibenzothiophenes residual concentration (analysis condition is as follows: 190 DEG C of column temperature,
220 DEG C of detector temperature, 220 DEG C of injector temperature, 1 μ L of sample volume).Desulfurization degree X is calculated according to formula (1), and draws isothermal suction
Attached curve:
In formula: X-simulation oil sample desulfurization degree；
C0- non-desulfurization front simulation oil sample sulfur content, mg/g
CtOil sample sulfur content, mg/g are simulated after-desulfurization
Ultrasonic time, H have been investigated by single_factor method2O2Dosage, reaction temperature and catalyst amount etc. are to resulting materials
The influence of catalytic oxidation desulfurization performance obtains optimal catalytic degradation condition, it may be assumed that 0.025g catalyst aoxidizes 50mL concentration and is
500mg/g simulates oil sample, and at 323K, n (O): n (S) is 8:1, and when ultrasonic time is 10min, catalysis degradation modulus reaches
88.13%；Catalysis degradation modulus only declines 2.51% after catalyst is reused 5 times, illustrates that the material has good catalysis de-
The performance and repeat performance of sulphur.
Application examples 2:
The ionic liquid loaded amination magnetic composite of 3 gained heteropoly acid of embodiment is applied to the catalysis of simulation oil sample
Oxidation sweetening.Step is the same as application examples 1.Ultrasonic time, H are optimized by response phase method2O2Dosage, reaction temperature and catalyst are used
The influence to the catalytic oxidation desulfurization performance of resulting materials such as amount, obtains optimal catalytic degradation condition, it may be assumed that 0.02g catalyst is urged
Changing oxidation 50mL concentration is that 500mg/g simulates oil sample, and at 323K, n (O): n (S) is 4:1, when ultrasonic time is 5min, catalysis
Degradation rate reaches 95.22%；Catalysis degradation modulus only declines 1.82% after catalyst is reused 5 times, and it is good to illustrate that the material has
The performance and repeat performance of good catalytic desulfurization, are the catalyst of function admirable.
The ionic liquid loaded amination magnetic composite of heteropoly acid of the present invention, is experimentally confirmed: invention behaviour
It is simple to make step, low in cost, the ionic liquid loaded amination magnetic composite of obtained heteropoly acid has jujube cake type structure；
Property is stablized, and can realize Magneto separate under external magnetic field；There is excellent catalytic desulfurization effect to the catalytic oxidation desulfurization of simulation oil sample,
It is potential high-quality catalyst.
Claims (10)
1. a kind of ionic liquid loaded amination magnetic composite of jujube cake type structure heteropoly acid, it is characterised in that: the composite wood
It includes heteropoly acid ionic liquid and amination magnetic composite that material, which prepares raw material, by ultrasonic immersing method by heteropoly acid ionic liquid
Body is carried on amination nano magnetic material, finally obtains the ionic liquid loaded amino nano magnetic composite materials of heteropoly acid.
2. a kind of ionic liquid loaded amination magnetic composite preparation method of jujube cake type structure heteropoly acid, it is characterised in that:
Step includes: to prepare heteropoly acid ionic liquid by using substitution reaction, prepare amination magnetic coupling material using solvent-thermal method
Material, then it is by ultrasonic immersing method that heteropoly acid is ionic liquid loaded on amination nano magnetic material, finally obtain heteropoly acid
Ionic liquid loaded amino nano magnetic composite materials.
3. jujube cake type structure heteropoly acid according to claim 2 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: prepare heteropoly acid ionic liquid, specifically are as follows: heat back N- methylimidazole or pyridine in magnetic agitation
Halogenated hydrocarbons is slowly added dropwise when stream, after being added dropwise, continues return stirring to complete reaction；It cools down after completion of the reaction, with acetic acid second
Ester repeatedly extracts excessive response raw material, and vacuum distillation removes remaining ethyl acetate, obtains ionic liquid；Further under stiring
Phosphotungstic acid aqueous solution is slowly added dropwise, continues to flow back after being added dropwise, be evaporated under reduced pressure after reaction, it is extra in reaction solution to remove
Moisture and by-product, it is dry to get arriving heteropoly acid ionic liquid.
4. jujube cake type structure heteropoly acid according to claim 3 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: the halogenated hydrocarbons is one of chloro or bromo-hydrocarbons of C4~C12；The N- methylimidazole or
The mass ratio of the material of pyridine and halogenated hydrocarbons is 0.5:1~1:5；The return stirring of the N- methylimidazole or pyridine and halogenated hydrocarbons
Reaction temperature be 60~150 DEG C, the reaction time be 2~for 24 hours；The phosphotungstic acid aqueous solution is saturated solution；The ion
The mass ratio of the material of liquid and phosphotungstic acid is 2:1~8:1；Continuing return time after being added dropwise is 2-12h；Drying temperature is
60-120 DEG C, the time be 2~for 24 hours.
5. jujube cake type structure heteropoly acid according to claim 4 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: the mass ratio of the material of the N- methylimidazole or pyridine and halogenated hydrocarbons is 1:1~1:2；N- methylimidazole
Or the return stirring reaction temperature of pyridine and halogenated hydrocarbons is 80~100 DEG C, the reaction time is 6~10h；Ionic liquid and phosphotungstic acid
The mass ratio of the material be 3:1~5:1；Continuing return time after being added dropwise is 6-10h；Drying temperature is 80-100 DEG C, time
For 6~10h.
6. jujube cake type structure heteropoly acid according to claim 2 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: preparation amination magnetic composite, specifically are as follows: ferric iron and acetate are dissolved in ethylene glycol；Three
The mass ratio of valence iron and acetate is 1:1~1:10, and mass concentration of the ferric iron in ethylene glycol is 20~400g/L, acetate
Mass concentration in ethylene glycol is 40~600g/L；5~30min is stirred at room temperature；Then organic polyamine 5-80mL is added,
Stirring is to forming stable orange solution；Reaction solution is transferred in reaction kettle, 100~240 DEG C of reactions 2~for 24 hours；After cooling
It is 7 that Magneto separate, which is washed to pH value, is dried in vacuo up to amination magnetic composite.
7. jujube cake type structure heteropoly acid according to claim 6 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: the ferric iron is one of ferric trichloride, ferric sulfate, and acetate is in sodium acetate or ammonium acetate
One kind；Mass concentration of the ferric iron in ethylene glycol is 40~120g/L, and quality of the acetate in ethylene glycol is dense
Degree is 60~180g/L, and organic polyamine is ethylenediamine, Diethylenetriamine, three second tetramines, a kind of in tetren, the use of organic polyamine
Amount is 20~60mL；Reaction temperature in reaction kettle is 150~200 DEG C, and the reaction time is 10~20h.
8. jujube cake type structure heteropoly acid according to claim 2 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: described prepares the ionic liquid loaded amination composite material of heteropoly acid, specifically are as follows: respectively by amino
Change magnetic composite ultrasonic disperse into aqueous solution, makes 5~100g/L of its mass concentration, it is above-mentioned to prepare heteropoly acid ionic liquid
Body is dissolved in acetone, makes 20~500g/L of its mass concentration, is slowly added dropwise to amination magnetic composite ultrasonic disperse
Into aqueous solution, so that the mass ratio of amination magnetic composite and heteropoly acid ionic liquid is 1:1~1:10；It is added dropwise
Continue 5~30min of ultrasound afterwards；After reaction, 2~24 hours are dried in vacuo at 30~100 DEG C to get to heteropoly acid ionic liquid
Body loads amination composite material.
9. jujube cake type structure heteropoly acid according to claim 2 ionic liquid loaded amination magnetic composite preparation side
Method, it is characterised in that: the mass concentration of the amination magnetic composite in water is 10~40g/L, and described is miscellaneous more
The mass concentration of acid ion liquid in acetone is 50~150g/L, the amination magnetic composite and heteropoly acid ion
The mass ratio of liquid is 1:4~1:6.
10. a kind of ionic liquid loaded amination composite material of heteropoly acid is specifically urged in the application of catalysis oil sample desulfurization
It is as follows to change sulfur method: under the conditions of shaken at room temperature, putting into the ionic liquid loaded amino of jujube cake type structure heteropoly acid of the invention
Change magnetic composite, dosage is that every rising mould intends the ionic liquid loaded amination magnetic composite dosage of heteropoly acid in oil sample
For 0.2~5g, ultrasound keeps its evenly dispersed, rapidly joins H2O2Solution 0.04-10mL, ultrasound after a certain period of time, in external magnetic field
Lower separating catalyst and simulation oil sample are acted on, 5mL acetonitrile extraction is taken；Under the conditions of 305-345K, oscillation rate is 100~300
Rev/min, the time is 30~180 minutes；Desulfurization degree can be greater than 85%.
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