CN104815695B - A kind of method that carbon nanotube loaded ionic-liquid catalyst catalysis prepares diisobutylene - Google Patents
A kind of method that carbon nanotube loaded ionic-liquid catalyst catalysis prepares diisobutylene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 39
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 76
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000011830 basic ionic liquid Substances 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- -1 compound ion Chemical class 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003805 vibration mixing Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 239000000047 product Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000006004 Quartz sand Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 12
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000011160 research Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000006384 oligomerization reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 239000002253 acid Substances 0.000 description 5
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- 239000010457 zeolite Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 235000013847 iso-butane Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000002229 CNT20 Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 101000685663 Homo sapiens Sodium/nucleoside cotransporter 1 Proteins 0.000 description 2
- 101000821827 Homo sapiens Sodium/nucleoside cotransporter 2 Proteins 0.000 description 2
- 101000822028 Homo sapiens Solute carrier family 28 member 3 Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 102100023116 Sodium/nucleoside cotransporter 1 Human genes 0.000 description 2
- 102100021541 Sodium/nucleoside cotransporter 2 Human genes 0.000 description 2
- 102100021470 Solute carrier family 28 member 3 Human genes 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- UEHUZQKLOWYOMO-UHFFFAOYSA-N diethylazanium;acetate Chemical compound CC(O)=O.CCNCC UEHUZQKLOWYOMO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000002011 CNT10 Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 101100328521 Schizosaccharomyces pombe (strain 972 / ATCC 24843) cnt6 gene Proteins 0.000 description 1
- AWKKZWAHGZUJMT-UHFFFAOYSA-J [Fe+2].[Ni+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound [Fe+2].[Ni+2].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] AWKKZWAHGZUJMT-UHFFFAOYSA-J 0.000 description 1
- LKDMDHMCNGRIAS-UHFFFAOYSA-N acetic acid;n-propylpropan-1-amine Chemical compound CC([O-])=O.CCC[NH2+]CCC LKDMDHMCNGRIAS-UHFFFAOYSA-N 0.000 description 1
- SVBXPEXMMWJPIE-UHFFFAOYSA-N acetic acid;propan-1-amine Chemical compound CCC[NH3+].CC([O-])=O SVBXPEXMMWJPIE-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- FVBHYZVVSXFCOO-UHFFFAOYSA-N tert-butyl hydrogen sulfate Chemical compound CC(C)(C)OS(O)(=O)=O FVBHYZVVSXFCOO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- AVBGNFCMKJOFIN-UHFFFAOYSA-N triethylammonium acetate Chemical compound CC(O)=O.CCN(CC)CC AVBGNFCMKJOFIN-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- AHCOTIVAMFIJQL-UHFFFAOYSA-N tripropylazanium;acetate Chemical compound CC(O)=O.CCCN(CCC)CCC AHCOTIVAMFIJQL-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of by using the carbon nanotube loaded ionic liquid-catalyzed method for preparing diisobutylene, the preparation method of the catalyst comprises the steps：S1：The process of CNT, CNT after being processed；S2：The preparation of basic ionic liquid；S3：The preparation of carbon nanotube loaded ionic-liquid catalyst.The catalyst is by so specific preparation method, compositional selecting etc. so as to achieve excellent catalytic effect, especially there is the high conversion of isobutene and the high selectivity of diisobutylene, and with good cyclical stability, have a good application prospect and industrial applications potentiality in petrochemical industry.
Description
Technical field
The present invention relates to a kind of synthetic method of olefin dimers, relates more particularly to a kind of carbon nanotube loaded ionic liquid
The method that body catalyst catalysis prepares diisobutylene, belongs to petrochemical industry.
Background technology
Diisobutylene is a kind of water white transparency, volatile liquid, and main component is 2,4,4- trimethyl -1- amylenes and 2,
4,4- trimethyl -2- amylenes, both theories compare for 4:1.In industrial goods, the former mass content is 76%, the matter of the latter
Amount content is about 20%, and other impurity mass content are about 4%.
Due to containing unsaturated double-bond in diisobutylene molecule, so with stronger reactivity, autohemagglutination can occur
Or multiple reactions such as copolyreaction, addition reaction or halogenating reaction, alkylated reaction, hydroxylating, so as to generating as pungent
Multiple fine-chemical intermediates such as base phenol, isononyl alcohol and octyldiphenylamine.
Just because of important function so, therefore, diisobutylene is a kind of important organising in organic chemical industry field
Work raw material, its can be used to prepare multiple compounds with extensive use, for example：
Diisobutylene (2,4,4- trimethyl -1- amylene mainly therein) and phenol are alkylated the pungent of reaction generation
Base phenol, is a kind of important fine chemical material, in addition to a series of nonionic surfactants are produced, can also produce oil-soluble phenol
Urea formaldehyde, vulcanizer, printing-ink, coating and preparation insulating varnish, antirust agent etc..
Diisobutylene can be used to produce polyisobutene relative nonlinear error, polyisobutene be mainly used as adhesive,
Electrical apparatus insulation material, encapsulant, lubricant tackifier, special white oil (high viscosity white oil can be replaced) etc..With lubricating oil, in
The demand of high-grade two cycle engine oil and other field to polyisobutene, the device for producing polyisobutene are more and more, to two
The demand of isobutene also will be increasing.
Corresponding with so vigorous demand and important function, China due to lack diisobutylene, so as to very big
Limit exploitation and the production of multiple downstream chemical products.
Therefore, the synthetic method of research and development diisobutylene is imperative to accomplish scale production, and the currently neck
Study hotspot in domain and important.Through the further investigation of researcher, multiple diisobutylene are have developed
Synthetic method, mainly has sulfuric acid extraction process, solid acid system etc., and solid acid system therein includes solid phosphoric acid method, sieve method again
Or resin method etc..
Sulfuric acid extraction process be to mix C4For raw material, using H2SO4Reacted for catalyst, the essence of reaction is that handle is mixed
Close C4In isobutene be dissolved in H2SO4In, the sulfuric acid tert-butyl ester is formed, then through being thermally formed diisobutylene.But the method
The dimer poor selectivity for obtaining, product purity are low and serious to equipment corrosion.At present, the method is eliminated.
Solid phosphoric acid method is industrial common method, and raw material is mixing C4In isobutene, with solid phosphoric acid as catalysis
Agent, carries out dimerization reaction in fixed bed reactors, and dimeric selectivity can reach 75% (see Yao Yaping, Yuan Meiqing, slowly
Cyanines et al., " T-49 novel solid phosphoric acid catalyst and its application ",《Petroleum refining and chemical industry》, 2000,31 (1), 10-14
Page).
As can be seen here, the traditional handicraft using sulfuric acid, p-methyl benzenesulfonic acid or solid phosphoric acid etc. as catalyst is all existed
Product selectivity is low, the low many drawbacks of purity.
In order to overcome drawbacks described above, China's Shijiazhuang Oil Refinery has introduced IFP (IFR) technique, in 1989
Year has been built up to mix C4(main component is isobutene, inertia C to cut4Iso-butane and part n-butene) it is raw material, selective folded
The process units of diisobutylene is produced in symphysis.The method is specially：C4Under alumina silicate bead catalytic action, (catalyst is adopted cut
The RCO that IFP and Beijing Research Institute of Petro-Chemical Engineering develop jointly2Alumina silicate pellet catalyst), using reaction of high order, in pressure
Under power 3.5-4.0MPa, make isobutene that oligomerisation to occur；C4N-butene in fraction hardly participates in reaction, isobutene almost all
Conversion, dimer selectively can reach 65% (see Chinese patent application CN1087616).
Additionally, people have also carried out substantial amounts of research to catalyst, such as zeolite molecular sieve catalyst has uniqueness
Pore passage structure, play the role of shape selective catalysis, show corrosion-free, heat resistance good, pollution-free the advantages of, so as to can be in alkene
Had an effect in the form of Bronsted acid in oligomerisation reaction.
(Duan Hongling, Liu Xuenuan, king mill are grand, " the isobutene oligomerisation reaction catalysis with modenite as carrier for Duan Hongling et al.
Agent research ",《China University Of Petroleum Beijing's journal (natural science edition)》2007,31 (2), the 121-125 page) have studied and boiled with mercerising
Stone is catalytic action of the catalyst of carrier to isobutene oligomerisation reaction, with NH in the method4NO3As ion exchanged soln,
The preparation conditions such as the acid site amount of modified mordenite, impregnation concentration, sintering temperature have been investigated on microreactor
On isobutene oligomerisation reaction conversion ratio and selective impact, suitable preparation condition has been obtained.
(Catherine S, Chen H, Robert F the B, " Shape-Selective such as Catherine
Oligomerization of Alkenes to Near-Linear Hydrocarbons by Zeolite Catalysis ",
《Journal of Catalysis》, 1996,161 (2), the 687-693 page) have studied molecular sieve HZSM-5 catalyzing iso-butane alkene
Oligomerisation reaction, it is found that the tetramer accounts for larger ratio in oligomerisation product.
Lu Yalin (Lu Yalin, " MCM-22 molecular sieve catalytic butene oligomerization repercussion study ",《Industrial Catalysis》, 2006,14
(3), the 14-16 page) synthesize porous material MCM-22 molecular sieve, which can be used for butene oligomerization reaction, find C8The choosing of alkene
Selecting property is more than 70%.
Kresnawahjuesa et al. (Kresnawahjuesa O, K ü hl G H, Gorte R J., " An
Examination ofAcid Sites in H-[Fe]ZSM-5for Olefin Oligomerization
And Adsorption ",《Journal of Catalysis》, 2002,210 (1), the 106-115 page) disclose nothing Al molecule
Sieve oligomerisation reaction performance of H- [Fe] ZSM-5 to 1- butylene.
But these zeolites occur in the duct of molecular sieve catalyst as the oligomerisation reaction of catalyst, as reaction is generated
Heavy polymer be difficult to diffuse out from duct, can often cause react duct obstruction, so as to cause molecular sieve catalytic
The fast deactivation of agent, the coking and deactivation for therefore how solving catalyst are the research emphasis of zeolite molecular sieve catalyst and difficult point.
In addition to zeolite, researcher finds that ion exchange resin can also be catalyzed C4The generation of olefin oligomerization, example
Such as：
Zhou Peng etc. (all boron, An Zengjian, Li Wenyan etc., " research of the isobutene oligomerisation reaction with Nafion as catalyst ",
《Jilin University's journal (Edition)》, 2003,41 (2), the 217-220 page) have studied catalysis of the Nafion to isobutene oligomerisation
Reactivity worth, Nafion are a kind of perfluorinated sulfonic resins of E.I.Du Pont Company's exploitation commercialization, and which has very strong acidity, permissible
There is oligomerisation reaction in catalyzing iso-butane alkene.The research found in the range of 30-60 DEG C, and the conversion ratio of isobutene is with the liter of reaction temperature
Height increases sharply, and during low temperature, product liquid is based on dimer；When reaction temperature is higher than 60 DEG C, product liquid with tripolymer is
Main.Nafion is supported on the carrier of Large ratio surface, more Isobutylene Dimers can be obtained at low temperature.
People, it was also found that in acid-exchange resin catalyzing iso-butane alkene dimerization, polar substances such as methyl alcohol and uncle
The presence of butanol can improve the selectivity of diisobutylene, but reduce the catalysis activity of ion exchange resin (see Honkela
M.L., Krause A O I, " Influence of polar components in the dimerization of
Isobutene ",《Catalysis Letters》, 2003,87 (3-4):113-119).And work as the water content in raw material and be
During 0.20-0.25mol/mol, the selectivity to isobutene dimer play an important role (see Talwalkar S, Chauhan M,
Aghalayam P,“Kinetic Studies on the Dimerization of Isobutene with Ion-
Exchange Resin in the Presence of Water as a Selectivity Enhancer ",
《Ind.Eng.Chem.Res》, 2006,45 (4), the 1312-1323 page).
In addition, it has been found that use SiO2、Al2O3Or SiO2-Al2O3Even load Ni, Co, Ge, Sn, Pb, Zn, Cu etc. are made and are urged
Agent, it is also possible to for being catalyzed the oligomerisation reaction of low-carbon alkene, such as (Zhang Xianhua, Fan Hongfei, Zhang He, " sulfuric acid such as Zhang Xianhua
III Fe of research of iron-nickel sulfate composite series alkene oligomerization catalyst(2/3)xNi(1-x)SO4-P2O5/γ-Al2O3Folded to 1- butylene
The catalytic performance of conjunction ",《Petroleum journal (PETROLEUM PROCESSING)》, 2000,16 (6), the 65-69 page) and the Fe that develops(2/3)xNi(1-x)SO4-
P2O5/γ-Al2O3Catalyst has higher butene oligomerization performance：The conversion ratio of 1- butylene is 85-95%, the choosing of dimerisation products
Selecting property is 80-90%, and the selectivity of trimerization product is 11-26%.
In addition to multiple catalysts described above, researcher finds acidic ion liquid while having the height of liquid acid
Density reaction active site and the fixedness of solid acid, its structure and acidity have adjustable denaturation, so as to can also be used for being catalyzed fourth
Alkene oligomerisation reaction, for example：
(Gu Y L, Shi F, Deng Y Q, " the SO3H-functionalized ionic liquid as such as Gu Yanlong
efficient,green and reusable acidic catalyst system for oligomerizaton of
Olefins ",《Catalysis Coummunication》, 2003,4, the 597-601 page) have studied with SO3H functionalization from
Oligomerisation reaction of the sub- liquid to isobutene, the ionic liquid both can also be used as solvent as catalyst, C8+C12Selection
Property higher than conventional solid acid catalyst.
The refined clear grade of poplar (Yang Shuqing, Liu Zhichang, Meng Xianghai etc., " research of ionic liquid-catalyzed isobutene oligomerisation reaction ",
《Petroleum refining and chemical industry》, 2007,38 (1), the 39-42 page) have studied AlCl3Ionic liquid and FeCl3Ionic liquid is to isobutyl
The catalytic performance of alkene oligomerisation.As a result show：The ionic liquid of anhydrous ferric trichloride and triethylamine hydrochloride synthesis has higher urging
Change activity and selectivity, under preferred process conditions, the conversion ratio of isobutene reaches more than 85%, C in liquid product8Alkene
Content is 2.87%, C12Olefin(e) centent is 57.43%.But in the method, in order to reduce the generation of high polymer, it is desirable in raw material
The concentration of isobutene can not be too high, needs plus substantial amounts of inert diluent, and stir speed (S.S.) is higher during the course of the reaction, with
Reduce the probability that the dimer of generation and raw material are reacted further.
In recent years, with the rapid raising of crude oil in China working ability and being continuously increased for ethylene yield, petrochemical industry pair
Products C4Resource is on the increase, but China is to C4The chemical utilization rate of resource is also relatively low.Mixing C4Isobutene majority in cut is used
In synthesizing methyl tertbutyl ether (MTBE), the blend component as motor petrol.In view of pollution of the MTBE to underground water, is mixing
C4It is significant that isobutene in cut seeks more rational utilization ways, it may have very important industrial significance and
Economic worth, and the study hotspot in the field and emphasis at present, all these is all the basis that the present invention is accomplished
It is located and power is leaned on.
Content of the invention
As described above, for the tight demand of the novel method for preparing diisobutylene, the present inventor has carried out depth to this
The research for entering, after a large amount of creative works are paid, so as to complete the present invention.
Specifically, one side, the present invention relates to a kind of preparation side of carbon nanotube loaded ionic-liquid catalyst
Method (i.e. for preparing the preparation method of the carbon nanotube loaded ionic-liquid catalyst of diisobutylene), the preparation method includes
Following steps：
S1：The process of CNT, CNT after being processed；
S2：The preparation of basic ionic liquid；
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst.
In the preparation method of the described carbon nanotube loaded ionic-liquid catalyst of the present invention, step S1 is concrete such as
Under, comprise the steps in other words：
S1-1：By CNT at 600-700 DEG C roasting 20-40 minute, then naturally cool to room temperature, obtain roasting
CNT afterwards；
S1-2：CNT after roasting is added in red fuming nitric acid (RFNA), is sufficiently stirred for, then filter, CNT is spent
Ionized water is fully washed, and is dry, so as to obtain CNT after described process.
Wherein, in step S1-1, by CNT at 600-700 DEG C roasting 20-40 minute, for example can for 600 DEG C,
Roasting 20 minutes, 30 minutes or 40 minutes at 650 DEG C or 700 DEG C.
Wherein, CNT belongs to very known material, can be obtained by multiple commercially available channels, and here is no longer one by one
Repeat.
Wherein, in step S1-2, the mass percent concentration of the red fuming nitric acid (RFNA) is 70-80%, for example can for 70%,
75% or 80%；The selection of its consumption belongs to the ordinary skill in the art, and those skilled in the art suitably can be selected,
This no longer repeats one by one.
In the preparation method of the described carbon nanotube loaded ionic-liquid catalyst of the present invention, step S2 is concrete such as
Under：
Binary compound ion liquid is mixed with tri-valent metal halides, and 20-30 minute is stirred at room temperature, so
After be warming up to 70-90 DEG C, and continuously stirred reaction 70-100 minute at such a temperature；After the completion of reaction, room temperature is naturally cooled to,
Dry, obtain the basis ionic liquid.
In step S2, the binary compound ion liquid is imidazole type ion liquid and acetic acid ammonium type ionic liquid
Mixture, both mol ratios are 1:2-3, for example, can be 1:2、1:2.5 or 1:3.
Wherein, the imidazole type ion liquid is selected from 1- ethyl-3-methylimidazole hexafluorophosphate, 1- normal-butyl -3- first
Base tetrafluoroborate, 1- normal-butyl -3- methylimidazole hexafluorophosphate, 1- normal-butyl -3- methylimidazole Bromide or 1,
3,1 '-three normal-butyl -2,2 '-bisglyoxaline hexafluorophosphate any one, most preferably 1,3,1 '-three normal-butyl -2,2 '-connection
Limidazolium hexafluorophosphate.
Wherein, the acetic acid ammonium type ionic liquid is acetic acid diethyl ammonium (can be described as diethyl amine acetate again), second triethylenetetraminehexaacetic acid
Ammonium (can be described as triethylamine acetate not only), positive third ammonium of acetic acid (can be described as n-propylamine acetate not only), positive third ammonium of acetic acid two (but also can claim
For di-n-propylamine acetate) or positive third ammonium of acetic acid three (can be described as Tri-n-Propylamine acetate again), most preferably positive third ammonium of acetic acid three.
In step S2, the tri-valent metal halides are AlCl3Or FeCl3.
In step S2, the binary compound ion liquid is 1 with the mol ratio of tri-valent metal halides:1.5-2.5,
Mole dosage sum and the trivalent metal halogen of i.e. described imidazole type ion liquid and the acetic acid ammonium type ionic liquid
The ratio of the mole dosage of compound is 1:1.5-2.5, described can be for example 1:1.5、1:2 or 1:2.5.
In step S2, under room temperature after stirring 20-30 minute, 70-90 DEG C is warming up to, for example, is warming up to 70 DEG C, 80 DEG C
Or 90 DEG C, and continuously stirred reaction 70-100 minute at such a temperature, such as 70 minutes, 80 minutes, 90 minutes or 100 minutes.
In the preparation method of the described carbon nanotube loaded ionic-liquid catalyst of the present invention, step S3 is concrete such as
Under：
The basic ionic liquid of CNT after the process of step S1 and step S2 is added in organic solvent, in room temperature
Under in the constant temperature oscillation case abundant vibration mixing 18-30 hour, filter, be vacuum dried 8-12 hour at 50-60 DEG C, so as to
Obtain the carbon nanotube loaded ionic-liquid catalyst.
In step S3, after the process, CNT is 1 with the mass ratio of the basis ionic liquid:0.1-0.4,
Can be for example 1:0.1、1:0.2、1:0.3 or 1:0.4.
In step S3, the organic solvent can be for example dichloromethane, chloroform, tetrahydrofuran, 2- methyl four
Any one of hydrogen furans, carbon tetrachloride etc. or any multiple mixture.
The consumption of the organic solvent is not particularly limited, if operation can be easy to, and after causing described process
CNT can carry out fully reaction with the basis ionic liquid, and those skilled in the art can be closed to the consumption
Suitable selection, this is no longer going to repeat them.
Second aspect, the present invention relates to the described carbon nanotube loaded ionic liquid prepared by said method is urged
Agent.
The inventors discovered that, the described carbon nanotube loaded ionic-liquid catalyst prepared by said method can use
Diisobutylene is prepared to be catalyzed, with excellent catalytic effect, purpose product can be obtained with high yield, have in petrochemical industry
There are good application prospect and value.
Therefore, the 3rd aspect, the present invention relates to a kind of preparation method of diisobutylene, methods described is with isobutene as original
Material, using the carbon nanotube loaded ionic liquid as catalyst.
In the preparation method, concrete operations are：First, isobutene carries out puffing, pressure control by pressure-reducing valve
Then system is dried by the drier equipped with 5A molecular sieve, enters back into preheater and be heated to 90-110 in 0.5-0.7MPa
DEG C, oligomerisation reaction is carried out finally by the fixed bed reactors equipped with the carbon nanotube loaded ionic liquid, product and not anti-
The isobutene that answers is condensed by condenser, and product is entered in collecting tank, is measured and subsequent analysis, and unreacted isobutyl
Alkene gas is circulated recycling.
As a kind of preferred embodiment, in the fixed bed reactors, be filled with from top to bottom ceramic ring (or quartz sand),
The mixture of the carbon nanotube loaded ionic-liquid catalyst and quartz sand, ceramic ring (or quartz sand), i.e., two ends are respectively
Ceramic ring (or quartz sand) and ceramic ring (or quartz sand), and centre is catalyst of the present invention and the mixture of quartz sand；
Wherein, in the mixture of the carbon nanotube loaded ionic-liquid catalyst and quartz sand, the catalyst and quartz sand
Mass ratio is 1:5.
As described above, the invention provides a kind of carbon nanotube loaded ionic-liquid catalyst, its preparation method and making
With the diisobutylene preparation method of the catalyst, the catalyst is by suitable compositional selecting, unique preparation method etc.
Obtain with excellent isobutene catalytic performance, for example excellent feed stock conversion, diisobutylene are selective, catalyst stabilization
Property etc., can solve the present situation of current China's diisobutylene yield wretched insufficiency, in petrochemical industry especially two isobutyl
Alkene preparation field has broad application prospects and industrial value.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction, more non-general to the real protection scope of the present invention
Protection scope of the present invention is confined to this.
The preparation of carbon nanotube loaded ionic-liquid catalyst
Preparation example 1：The preparation of catalyst CNT1
S1：The process of CNT, CNT after being processed
S1-1：By CNT at 600 DEG C roasting 40 minutes, then naturally cool to room temperature, after obtaining roasting, carbon is received
Mitron；
S1-2：CNT after roasting is added in the appropriate red fuming nitric acid (RFNA) that mass percent concentration is 70%, is fully stirred
Mix, then filter, CNT deionized water is fully washed, dry, so as to obtain CNT after described process.
S2：The preparation of basic ionic liquid
Mol ratio is 1:2 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate and positive third ammonium of acetic acid three
Mixture (i.e. binary compound ion liquid) and AlCl3Mixed (wherein, the binary compound ion liquid and AlCl3Rub
You are than being 1:1.5), and it is stirred at room temperature 20 minutes, 90 DEG C is then heated to, and 70 points of continuously stirred reaction at such a temperature
Clock；After the completion of reaction, room temperature is naturally cooled to, dry, obtain the basis ionic liquid.
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst
By the basic ionic liquid of CNT after the process of step S1 and step S2 according to mass ratio be 1:0.1 ratio
Be added in q. s. methylene chloride, fully mixing 18 hours is vibrated in constant temperature oscillation case at room temperature, filter, at 50 DEG C
Vacuum drying 12 hours, so as to obtain the carbon nanotube loaded ionic-liquid catalyst, is named as CNT1.
Preparation example 2：The preparation of catalyst CNT2
S1：The process of CNT, CNT after being processed
S1-1：By CNT at 650 DEG C roasting 30 minutes, then naturally cool to room temperature, after obtaining roasting, carbon is received
Mitron；
S1-2：CNT after roasting is added in the appropriate red fuming nitric acid (RFNA) that mass percent concentration is 75%, is fully stirred
Mix, then filter, CNT deionized water is fully washed, dry, so as to obtain CNT after described process.
S2：The preparation of basic ionic liquid
Mol ratio is 1:2.5 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate and positive third ammonium of acetic acid three
Mixture (i.e. binary compound ion liquid) and FeCl3Mixed (wherein, the binary compound ion liquid and FeCl3's
Mol ratio is 1:2), and it is stirred at room temperature 30 minutes, 70 DEG C is then heated to, and continuously stirred reaction 100 at such a temperature
Minute；After the completion of reaction, room temperature is naturally cooled to, dry, obtain the basis ionic liquid.
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst
By the basic ionic liquid of CNT after the process of step S1 and step S2 according to mass ratio be 1:0.3 ratio
Be added in appropriate carbon tetrachloride, fully mixing 25 hours is vibrated in constant temperature oscillation case at room temperature, filter, at 55 DEG C
Vacuum drying 10 hours, so as to obtain the carbon nanotube loaded ionic-liquid catalyst, is named as CNT2.
Preparation example 3：The preparation of catalyst CNT3
S1：The process of CNT, CNT after being processed
S1-1：By CNT at 700 DEG C roasting 20 minutes, then naturally cool to room temperature, after obtaining roasting, carbon is received
Mitron；
S1-2：CNT after roasting is added in the appropriate red fuming nitric acid (RFNA) that mass percent concentration is 80%, is fully stirred
Mix, then filter, CNT deionized water is fully washed, dry, so as to obtain CNT after described process.
S2：The preparation of basic ionic liquid
Mol ratio is 1:3 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate and positive third ammonium of acetic acid three
Mixture (i.e. binary compound ion liquid) and AlCl3Mixed (wherein, the binary compound ion liquid and AlCl3Rub
You are than being 1:2.5), and it is stirred at room temperature 25 minutes, 80 DEG C is then heated to, and 80 points of continuously stirred reaction at such a temperature
Clock；After the completion of reaction, room temperature is naturally cooled to, dry, obtain the basis ionic liquid.
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst
By the basic ionic liquid of CNT after the process of step S1 and step S2 according to mass ratio be 1:0.4 ratio
Be added in appropriate tetrahydrofuran, fully mixing 30 hours is vibrated in constant temperature oscillation case at room temperature, filter, at 60 DEG C
Vacuum drying 8 hours, so as to obtain the carbon nanotube loaded ionic-liquid catalyst, is named as CNT3.
Preparation example 4：The preparation of catalyst CNT4
S1：The process of CNT, CNT after being processed
S1-1：By CNT at 650 DEG C roasting 40 minutes, then naturally cool to room temperature, after obtaining roasting, carbon is received
Mitron；
S1-2：CNT after roasting is added in the appropriate red fuming nitric acid (RFNA) that mass percent concentration is 70%, is fully stirred
Mix, then filter, CNT deionized water is fully washed, dry, so as to obtain CNT after described process.
S2：The preparation of basic ionic liquid
Mol ratio is 1:2.5 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate and positive third ammonium of acetic acid three
Mixture (i.e. binary compound ion liquid) and FeCl3Mixed (wherein, the binary compound ion liquid and FeCl3's
Mol ratio is 1:2), and it is stirred at room temperature 30 minutes, 75 DEG C is then heated to, and 90 points of continuously stirred reaction at such a temperature
Clock；After the completion of reaction, room temperature is naturally cooled to, dry, obtain the basis ionic liquid.
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst
By the basic ionic liquid of CNT after the process of step S1 and step S2 according to mass ratio be 1:0.2 ratio
Be added in appropriate tetrahydrofuran, fully mixing 22 hours is vibrated in constant temperature oscillation case at room temperature, filter, at 50 DEG C
Vacuum drying 11 hours, so as to obtain the carbon nanotube loaded ionic-liquid catalyst, is named as CNT4.
Preparation example 5-12：The preparation of catalyst CNT5-CNT12
Preparation example 5-8：CNT the step of respectively by preparation example 1-4 in S1 is (i.e. straight in addition to not carrying out calcination process
Connecing carries out red fuming nitric acid (RFNA) process by CNT), other operations are all constant, so as to respectively sequentially with the phase Tongfang with preparation example 1-4
Formula and implement preparation example 5-8, the catalyst for obtaining sequentially is named as CNT5, CNT6, CNT7 and CNT8.
Preparation example 9-12：CNT the step of respectively by preparation example 1-4 in S1 do not carry out red fuming nitric acid (RFNA) process in addition to (i.e.
To be directly used in step S3 after CNT calcination process), other operations are all constant, so as to respectively sequentially with preparation example 1-
4 same way and implement preparation example 9-12, the catalyst for obtaining sequentially is named as CNT9, CNT10, CNT11 and CNT12.
Preparation example 13-16：The preparation of catalyst CNT13-CNT16
Removing respectively by 1,3,1 '-three normal-butyls -2,2 in S2 the step of preparation example 1-4 '-bisglyoxaline hexafluorophosphate replaces
It is changed to outside following imidazole type ion liquid, other operations are all constant, so as to implement preparation example 13-16, the imidazoles that used
The name of type ionic liquid, corresponding relation and catalyst see the table below.
Preparation example 17-20：The preparation of catalyst CNT17-CNT20
Except respectively positive for acetic acid three in S2 the step of preparation example 1-4 third ammonium being replaced with following acetic acid ammonium type ionic liquid
Outward, other operations are all constant, so as to implement preparation example 17-20, the acetic acid ammonium type ionic liquid that used, corresponding relation and urge
Agent name see the table below.
Preparation example 21-28：The preparation of catalyst CNT21-CNT28
Preparation example 21-24：Remove and respectively the binary compound ion liquid in S2 the step of preparation example 1-4 is replaced with single group
Divide 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate (its mole dosage mole dosage still for original two kinds of components
Sum) outward, other operations are all constant, so as to sequentially implement preparation example 21- respectively with the same way with preparation example 1-4
24, the catalyst for obtaining sequentially is named as CNT21, CNT22, CNT23 and CNT24.
Preparation example 25-28：Remove and respectively the binary compound ion liquid in S2 the step of preparation example 1-4 is replaced with single group
Outward, other operations are all constant to divide positive third ammonium of acetic acid three (its mole dosage mole dosage sum still for original two kinds of components), from
And sequentially implementing preparation example 25-28 respectively with the same way with preparation example 1-4, the catalyst for obtaining sequentially is named as
CNT25, CNT26, CNT27 and CNT28.
The carbon nanotube loaded ionic liquid-catalyzed method for preparing diisobutylene
Using the carbon nanotube loaded ionic-liquid catalyst of the difference of gained of the present invention, implement with isobutene as raw material
The preparation of diisobutylene, all so as to investigate catalytic capability and stability of different carbon nanotube loaded ionic-liquid catalysts etc.
The quality of many performances.
Concrete course of reaction
, using the micro fixed-bed reactor of stainless steel, the fixed bed is anti-for the oligomerisation reaction of isobutene of the present invention
A diameter of 14mm of device is answered, and thermocouple is inserted in the center sleeve of reactor to detect and controlling reaction temperature, reaction pressure
By voltage-stabilizing system control.
In the fixed bed reactors, it is filled with ceramic ring, the carbon nanotube loaded ionic liquid from top to bottom and urges
The mixture of agent and quartz sand, quartz sand, i.e. two ends are respectively ceramic ring and quartz sand, and middle is catalyst of the present invention
Mixture with quartz sand；Wherein, in mixture of the carbon nanotube loaded ionic-liquid catalyst with quartz sand, described
Catalyst is 1 with the mass ratio of quartz sand:5.
First, isobutene carries out puffing by pressure-reducing valve, Stress control in 0.6MPa, then by being equipped with 5A molecule
The drier of sieve is dried, and enters back into preheater and is heated to 100 DEG C, and feed rate is 2.0ml/ minute, so as to by fixing
Bed reactor carries out oligomerisation reaction, and product and unreacted isobutene are condensed by condenser, and product is entered in collecting tank, is carried out
Metering and subsequent analysis, and unreacted isobutene gas are circulated recycling.
By the product that collects by be configured with fid detector SP3420 gas chromatograph (Beijing Analytical Instrument Factory) and
Its composition analyzed by Trace GC/DSQ mass spectrograph (Finnigan company of the U.S.).
The catalytic performance of different catalysts
All according to above-mentioned concrete course of reaction, the catalytic performance under the conditions of carrying out same process to different catalysts is surveyed
Examination, concrete outcome see the table below 1.
Table 1：The performance data of different catalysts
Note：" C therein16+Alkene " refers to C16And the selectivity of above alkene
From upper table 1, the carbon nanotube loaded ionic-liquid catalyst of the present invention has excellent isobutene and prepares two
Catalytic performance required for isobutene, the conversion ratio up to 95% or so of isobutene, the selectivity of diisobutylene is up to 86.7-
87.4%.
In contrast to this be：
1st, when calcination process is not carried out to CNT or red fuming nitric acid (RFNA) is processed, catalytic performance is all caused to decrease, but
Non- calcination process causes performance reduction become apparent from processing (see CNT5-CNT8 and CNT9-CNT12) in unused red fuming nitric acid (RFNA), this
Prove that CNT is not only simply and load effect is played, the difference of its pre-treating method can be significantly affected finally
The catalytic performance of catalyst；
2nd, when the species of the imidazole type ion liquid changed in binary compound ion liquid or acetic acid ammonium type ionic liquid,
All cause catalytic performance to have to reduce (see CNT13-CNT16 and CNT17-CNT20) further, this proves loaded 1,3,
1 '-three normal-butyl -2,2 '-bisglyoxaline hexafluorophosphate and positive third ammonium of acetic acid three can play best concerted catalysis effect, when changing
When becoming any of which, even with the second triethylenetetraminehexaacetic acid ammonium very similar with positive third ammonium of acetic acid three or positive third ammonium of acetic acid two,
Also catalytic performance is all caused to significantly reduce；
3rd, from CNT21-CNT24 and CNT25-CNT28, although using 1,3,1 '-three normal-butyl -2 of one-component,
Catalytic performance during 2 '-bisglyoxaline hexafluorophosphate will be significantly better than using catalytic during one-component three positive third ammonium of acetic acid
Can, but the catalytic performance of both has and is the most significantly greatly lowered, and this is proved only while preferred using both
Component, could play unexpected concerted catalysis effect each other.
The cyclical stability performance of different catalysts
All according to above-mentioned concrete course of reaction, the cyclical stability under the conditions of same process is carried out to different catalysts
Can test, specifically after persistently carrying out reacting 150 hours, measure the selection that isobutene conversion is purpose product diisobutylene
Property, so as to its cyclical stability of quantitative expedition, concrete outcome see the table below 2.
Table 2：The stable circulation performance of different catalysts
As can be seen here, the catalyst of the present invention has excellent cyclical stability, after reaction 150 hours, still has
There are the isobutene conversion of 86.4-88.1% and the diisobutylene selectivity of 82.1-83.2%；And the raw material of other catalyst turns
Rate and purpose product selectively all have significant substantially reduce, especially with one-component ionic liquid when reduction
Degree becomes apparent from；All these all demonstrates that only could to obtain best circulation using the catalyst of the present invention steady
Qualitative.
In sum, clearly can be found out by above-mentioned all embodiments, the invention provides one kind is by using CNT
The method that supported ion liquid catalysis prepares diisobutylene, the catalyst by specific preparation method, compositional selecting etc. from
And excellent catalytic effect is achieved, especially there is the high conversion of isobutene and the high selectivity of diisobutylene, and tool
There is good cyclical stability, so as to have a good application prospect and industrial applications potentiality in petrochemical industry.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents for having read the present invention, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor limited by the application appended claims
Within the scope of shield.
Claims (5)
1. a kind of preparation method of carbon nanotube loaded ionic-liquid catalyst, the preparation method comprise the steps：
S1：The process of CNT, CNT after being processed；
S2：The preparation of basic ionic liquid；
S3：The preparation of carbon nanotube loaded ionic-liquid catalyst；
Step S1 comprises the steps：
S1-1：By CNT at 600-700 DEG C roasting 20-40 minute, then naturally cool to room temperature, obtain carbon after roasting
Nanotube；
S1-2：CNT after roasting is added in red fuming nitric acid (RFNA), is sufficiently stirred for, then filter, by CNT deionization
Water is fully washed, and is dry, so as to obtain CNT after described process；
Step S2 is specific as follows：
Binary compound ion liquid is mixed with tri-valent metal halides, and 20-30 minute, Ran Housheng is stirred at room temperature
Temperature is to 70-90 DEG C, and continuously stirred reaction 70-100 minute at such a temperature；After the completion of reaction, room temperature is naturally cooled to, do
Dry, obtain the basis ionic liquid；
The binary compound ion liquid is the mixture of imidazole type ion liquid and acetic acid ammonium type ionic liquid, both mole
Than for 1:2-3；
The imidazole type ion liquid is 1,3,1 '-three normal-butyls -2,2 '-bisglyoxaline hexafluorophosphate；
The acetic acid ammonium type ionic liquid is positive third ammonium of acetic acid three.
2. preparation method as claimed in claim 1, it is characterised in that：The tri-valent metal halides are AlCl3Or FeCl3.
3. the preparation method as described in any one of claim 1-2, it is characterised in that：Step S3 is specific as follows：
The basic ionic liquid of CNT after the process of step S1 and step S2 is added in organic solvent, at room temperature in
In constant temperature oscillation case, fully vibration mixing 18-30 hour, filtration, is vacuum dried 8-12 hour, so as to obtain at 50-60 DEG C
The carbon nanotube loaded ionic-liquid catalyst.
4. the carbon nanotube loaded ionic-liquid catalyst that preparation method according to any one of claim 1-3 is prepared.
5. a kind of preparation method of diisobutylene, it is characterised in that：Methods described with isobutene as raw material, with claim 4
The carbon nanotube loaded ionic-liquid catalyst is used as catalyst.
Priority Applications (1)
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| "Highly efficient trimerization of isobutene over silica supported chloroaluminate ionic liquid using C4 feed";Shimin Liu et al;《Catalysis Today》;20120724;第200卷;第2.1节，第2.3节，Table 2 * |
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