CN101200404A - Method for synthesizing short-chain olefin by ethylene oligomerization - Google Patents
Method for synthesizing short-chain olefin by ethylene oligomerization Download PDFInfo
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- CN101200404A CN101200404A CNA2007100312709A CN200710031270A CN101200404A CN 101200404 A CN101200404 A CN 101200404A CN A2007100312709 A CNA2007100312709 A CN A2007100312709A CN 200710031270 A CN200710031270 A CN 200710031270A CN 101200404 A CN101200404 A CN 101200404A
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- ethylene oligomerization
- catalyzer
- ethylene
- catalyst
- ionic liquid
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000005977 Ethylene Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006384 oligomerization reaction Methods 0.000 title claims description 80
- 150000001336 alkenes Chemical class 0.000 title claims description 13
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- -1 olefin hydrocarbon Chemical class 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000001819 mass spectrum Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 238000001636 atomic emission spectroscopy Methods 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 abstract 1
- 229920001542 oligosaccharide Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 74
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 39
- 238000006116 polymerization reaction Methods 0.000 description 27
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000007306 functionalization reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000002051 biphasic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 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
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for a short chain olefin hydrocarbon through an ethylene oligomeric. The invention is characterized in that: the dual salicylaldehyde imine nickel catalyst is loaded in imidazole Al-ionic ionic liquid; under the assistant catalysis of AlEt2Cl, the ethylene oligosaccharide can be catalyzed in two phase in a mild reaction condition. Comparing with a homogeneous system, the activity of the catalyst system in the ionic liquid can be improved greatly; all generative products are ethylene oligomeric, and the production can be separated through a simple settlement. The ionic liquid of the catalyst can be recycled by being dissolved. The reaction condition has no great impact to the distribution of the oligomeric production. The test result of gas chromatography mass spectrum that the ethylene oligomeric production mainly is a short chain olefin hydrocarbon with the carbon atom of less than 10. Compared with the tradition of salicylaldehyde imine nickel catalyst 1 and 2, the catalyst 3 and 4 after the ion function has a higher activity and a better thermal stability. The test for atomic emission spectroscopy of the plasma shows that the recovery rate of catalyst 1 and 2 can be more than 98 percent, while that of the catalyst 3 and 4 after the ion function can reach 99.9 percent.
Description
Technical field
The present invention relates to the olefin oligomerization field, specifically, relate to a kind of method of utilizing the catalyst ethylene oligomerization to prepare short chain olefin.
Background technology
Ethylene oligomerization is an important petroleum chemical industry, is a class important chemical material by ethylene oligomerization synthetic short chain olefin, according to different chain lengths, has been widely used at aspects such as washing composition, softening agent, lubricating oil, tensio-active agents.In addition, linear alpha-alkene (LAO) can be used as comonomer (as 1-butylene, 1-hexene and 1-octene), prepares the branched polyethylene (LLDPE) or the elastomer material of various commercial brand with ethylene copolymer.
The aluminum alkyl catalyst that present industrial ethylene oligomerization catalyzer mainly is BP Amoco, the nickel catalyzator of the SHOP technology of Shell company, and the chrome catalysts of Phillips.In SHOP technology, nickel catalyzator is dissolved in 1, in the 4-butyleneglycol, forms the biphasic catalysis system, and products therefrom is easy to separate, and catalyzer can recycle.In the last few years, a large amount of documents and patent had reported also that the highly selective catalyzed ethylene was oligomeric with novel transition metal title complex (mainly concentrating on metallic nickel, iron and chromium metal complexes) high reactivity in the homogeneous phase organic solvent.But for these homogeneous catalysis systems, usually need expensive promotor MAO, and nonpolar solvent is often smaller to the solubleness of metal complexes, after reaction is finished, catalyzer separates relatively difficulty with product, catalyzer also is difficult to recycle or recycling.
As the green solvent ionic liquid organometallics is had very good solubility, its high polarity makes it and general non-polar solvent not dissolve each other.Therefore by the useful load of ionic liquid to metal catalyst, can realize liquid-liquid biphasic catalysis system efficient catalytic reaction, and catalyzer can reclaim and recycle, reaction product is easy to separate.
The report that carries out olefin oligomerization in ionic liquid was just arranged as far back as nineteen ninety, Chauvin etc. have just at first studied the dimerization reaction of nickel complex catalyzing propone in chlorine aluminic acid type ionic liquid, the nickel catalyzing butene dimerization processes (Dimersol process) of France Petroleum Institute (IFP) development research has entered the industrial test stage, at present, some metallic nickel title complexs biphasic catalysis alkene (ethene in ionic liquid that mainly contained Chauvin, Wasserscheid and three group studies of Dupont, propylene, 1-butylene) oligomeric.The catalyzer that uses mainly is organic nickel salt, as [Ni (MeCN)
6] [BF
4]
2, (COD) Ni (hFacac), NiL
2Cl
2(L:P (Bu)
3, P (i-Pr)
3, P (cyclohexyl)
3, pyridine) etc.These catalyzer generally are difficult to synthesize poor stability; And selected ionic liquid is difficult to synthesize, and costs an arm and a leg.
Summary of the invention
The objective of the invention is to overcome existing olefin oligomerization technology exists catalyzer to be difficult to synthesize, poor stability, and problems such as catalyzer and product separation difficulty, a kind of method of synthesizing short-chain olefin by ethylene oligomerization is provided, this synthetic method adopts the catalyzer with high reactivity and good stability, and realize that catalyzer is easy to separate with product, catalyst system that can recycling.
A kind of method of synthesizing short-chain olefin by ethylene oligomerization, it is synthetic by the effect that loads on the catalyzer in the ionic liquid ethylene oligomerization reaction to take place down, and described catalyzer is made up of double salicylaldehyde imine nickel complex and aluminum alkyls, and both mol ratios are 1: 100～900.The preferred molar ratio of double salicylaldehyde imine nickel complex and aluminum alkyls is 1: 400～700.
Catalyst activity TOF maintains 10
4Mol ethene/(molNih).The gained oligomerization product is mainly short chain olefins such as butylene, hexene, octene, does not have superpolymer to generate in the product.
The structural formula of above-mentioned double salicylaldehyde imine nickel complex is suc as formula (I).
R wherein
1Can be hydrogen atom or alkyl, R
2It can be the substituting group of alkyl, aromatic substituent or band imidazol ion functional group.
Described aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or ethyl aluminum dichloride.Preferred aluminium diethyl monochloride.
Described ionic liquid is an aluminic acid type imidazoles, and its structural formula is
Or
N is 1 to 3.
R wherein
3And R
4Be the alkyl of different chain length degree, R
3Preferable methyl, R
4Preferred butyl, the negatively charged ion of aluminium can be AlCl
4 -, Al
2Cl
7 -Or its mixture, it can pass through AlCl
3Dosage regulated control.
The solvent that forms the oligomeric system of two-phase with ionic liquid can be the inertia aromatic solvent, toluene for example, benzene; Also can be straight-chain paraffin, hexane for example, heptane etc., or halohydrocarbon, chlorobenzene for example, chloroform.
Compared with prior art, the present invention has following beneficial effect: the present invention adopts two kinds of common double salicylaldehyde imines nickel type catalyzer 1,2, and the double salicylaldehyde imines nickel type catalyzer 3 of two kinds of new functionizations, 4, and these four catalyst cupports in imidazoles aluminic acid type ionic liquid, at AlEt
2Under the Cl promoting catalysis, under the gentle reaction conditions, the biphasic catalysis ethylene oligomerization.Compare with the oligomeric technology of traditional homogeneous ethylene, products therefrom is an ethylene low polymer all, and catalytic activity is greatly improved, and product is promptly separable by simple sedimentation, and catalyzer can the recirculation utilization.In addition, reaction conditions (as temperature of reaction, aluminium nickel ratio) is little to the oligomerization product distribution influence, and the composition of resultant product does not have big variation basically.Gas chromatography-mass spectrum (GC-MS) test result shows that the ethylene oligomerization product is mainly carbon atom and is not more than 10 short chain olefin.With respect to traditional salicylic alidehyde imine nickel catalyzator 1,2, the double salicylaldehyde imines nickel type catalyzer 3,4 after the ion functionalization has higher activity, better thermostability.ICP-AES test (ICP) shows, 1,2 the rate of recovery can reach＞and 98%, and catalyzer 3,4 rate of recovery after the ion functionalization can reach 99.9%.
Embodiment
Embodiment 1: aluminic acid type imidazole ion liquid synthetic
Under the anhydrous and oxygen-free condition, under 0 ℃, get the anhydrous AlCl of 30.5g
3(0.229mol) join in 33.3g chlorination 1-butyl-3-Methylimidazole (0.191mol), be warming up to 40 ℃ then, stirring is spent the night, and promptly obtains mol ratio and be 1.2 imidazoles aluminic acid type ionic liquid.
Embodiment 2: double salicylaldehyde amine imines nickel compound 1 synthetic
The salicylic aldehyde of 1ml (12.9mmol) joins and contains 6.85g (38.7mmol) 2,6-diisopropyl aniline, 1.60g Ni (OAc)
24H
2In the 100ml ethanolic soln of O (6.45mmol), reflux 4h is cooled to room temperature, generates a large amount of green crystals, filters, and recrystallization obtains the fine particulate green crystal in normal heptane, is weighed as 2.62g, productive rate 65.6%.Ultimate analysis (is pressed C
38H
44N
2NiO
2Calculate, %), theoretical value: C, 73.68, H, 7.16, N, 4.52; Measured value: C, 73.66, H, 7.31, N, 4.43.
Embodiment 3: double salicylaldehyde amine imines nickel compound 2 synthetic
The salicylic aldehyde of 1ml (12.9mmol) joins and contains 2.28g (38.7mmol) Tri N-Propyl Amine, 1.60gNi (OAc)
24H
2In the 100ml ethanolic soln of O (6.45mmol), reflux 4h is cooled to room temperature, generates a large amount of green crystals, filters, and recrystallization obtains the particulate state green crystal in normal heptane, is weighed as 1.55g, productive rate 62.8%.Ultimate analysis (is pressed C
20H
24N
2NiO
2Calculate, %), theoretical value: C, 62.70, H, 6.31, N, 7.31; Measured value: C, 62.68, H, 6.41, N, 7.29.
Embodiment 4: functionalization double salicylaldehyde amine imines nickel compound 3 is synthetic
Functionalization salicylic aldehyde amine imine ligand L
3Synthetic
The hydrobromate (25.8mmol) of the 3-bromine propylamine of the salicylic aldehyde of 2ml (25.8mmol) and 5.65g joins 100ml and contains in 95% the ethanolic soln of 1.20gNaOH (30mmol) stirring heating backflow 4h.Be cooled to room temperature, add the distilled water of 100ml, bottom settlings goes out a certain amount of yellow substance, and separatory obtains the yellow viscous liquid of 5.50g, is intermediate product 2-(HO) C
6H
4CH=NCH
2CH
2CH
2The thick product of Br.Productive rate 88% (22.7mmol).2-(HO) C
6H
4CH=NCH
2CH
2CH
2Br further adds 1-Methylimidazole 1.90g (23.2mmol) without purification, 50ml normal hexane, 50ml ether, reflux 3 days.Cooling, the bottom obtains the gel yellow solid, topples over the top organic solvent.And then with a large amount of ether washings bottom yellow substance, heat 120 ℃ of vacuum at last and drain 12h, obtain yellow solid product L
3Weigh 6.23g, productive rate 74.5%.Mass spectrum EI-MS (m/z): 244.2[M]
+Ultimate analysis (is pressed C
14H
18BrN
3O calculates, %), and theoretical value: C, 51.86, H, 5.60, N, 12.96; Measured value: C, 51.10, H, 5.72, N, 12.70.Nmr analysis
1H NMR (300MHz, CDCl
3, 25 ℃): δ 12.84 (1H, s, OH), 10.31 (1H, s, NCHN), 8.51 (1H, s, CH=N), 7.52 (1H, s, Ph-H), 7.34-7.33 (3H, m, Ph-H), 6.84-6.88 (2H, m, NCHCHN), 4.55 (2H, t, NCH
2), 3.89 (3H, s, CH
3), 3.81 (3H, t, NCH
2), 2.40 (2H, m, CH
2).
13C?NMR(75MHz，CDCl
3，25℃)：166.49，160.49，137.18，132.37，131.66，123.30，122.10，118.73，118.27，116.51，56.22，48.38，36.55，30.96。
Functionalization double salicylaldehyde amine imines nickel compound 3 is synthetic
Under the nitrogen atmosphere, get ligand L
31.5g (4.63mmol) join and contain 0.575g Ni (OAc)
2.4H
2In 30 ethanolic solns of O (2.31mmol), reflux 4h, cooling is drained and is obtained green flour powder material, uses methylene dichloride (10ml * 3) respectively, and ether (20ml * 3) washing six times is drained and is obtained green flour powder double salicylaldehyde amine imines nickel compound 3.Be weighed as 1.38g.Productive rate 84.5%.Ultimate analysis (is pressed C
28H
34Br
2N
6NiO
2Calculate, %), theoretical value: C, 47.69, H, 4.86, N, 11.92;
Measured value: C, 46.88H, 5.01N, 11.64.
1H?NMR(300MHz，DMSO-d
6，25℃)：δ9.28(2H，s，NCHN)，8.45(2H，s，CH＝N)，7.02-7.97(8H，m，Ph-H)，6.57-7.40(4H，m，NCHCHN)，4.24(4H，m，NCH2)，3.80(6H，s，NCH
3)，3.61(4H，m，NCH
2)，2.17(4H，m，CH
2)。
Embodiment 5: functionalization double salicylaldehyde amine imines nickel compound 4 synthetic
Functionalization salicylic aldehyde amine imine ligand L
4Synthetic
3 of 5g, the hydrobromate (21.4mmol) of the 3-bromine propylamine of 5-di-tert-butyl salicylaldehyde (21.4mmol) and 4.69g join 100ml and contain in 95% the ethanolic soln of 1.00gNaOH (25mmol) stirring heating backflow 4h.Add the distilled water of 100ml, bottom settlings goes out a certain amount of yellow viscous liquid, and 75 ℃ of following separatory obtain lower floor's yellow substance, and the cooling back is a sticky solid, is weighed as 6.46g, is intermediate product 3,5-
tBu
2-2-(HO) C
6H
4CH=NCH
2CH
2CH
2The thick product of Br, productive rate 85.2% (18.2mmol).3,5-
tBu
2-2-(HO) C
6H
4CH=NCH
2CH
2CH
2Br further adds 1-Methylimidazole 1.50g (18.3mmol) without purification, 50ml normal hexane, 50ml ether, reflux 3days.Cooling, the bottom obtains yellow solid, topples over the top organic solvent.And then with a large amount of ether washings bottom yellow substance, heat 120 ℃ of vacuum at last and drain 12h, obtain yellow powder shape solid product L
4Weigh 6.92g, productive rate 74.1%.Mass spectrum EI-MS (m/z): 356.5[M]
+Ultimate analysis (is pressed C
22H
34BrN
3O calculates, %), and theoretical value: C, 60.54, H, 7.85, N, 9.63; Measured value: C, 60.25 H, 8.019, N, 9.521.Nmr analysis
1H NMR (300MHz, CDCl
3, 25 ℃): δ 13.13 (1H, s, OH), 10.75 (1H, s, NCHN), 8.51 (1H, s, CH=N), 7.35 (1H, d, Ph-H), 7.25 (1H, s, Ph-H), 7.16 (1H, d, NCH), 7.08 (1H, s, NCH), 4.60 (2H, t, NCH
2), 3.85 (2H, m, CH
2CH
2), 3.80 (3H, s, CCH
3), 2.40 (2H, m, CH
2), 1.42 (9H, s, C (CH
3)
3), 1.30 (9H, s, C (CH
3)
3).
13C?NMR(75MHz，CDCl
3，25℃)：δ167.52，157.32，140.36，137.71，136.22，127.05，126.25，123.01，121.77，117.38，56.34，48.60，36.44，34.94，34.13，31.44，30.89，29.37。
Synthesizing of functionalization double salicylaldehyde amine imines nickel compound 4
Under the nitrogen atmosphere, get ligand L
41.5g (3.44mmol) join and contain 0.425g Ni (OAc)
24H
2In 30 ethanolic solns of O (1.71mmol), reflux 4h, cooling, drain and obtain green flour powder material, this powdery substance recrystallization in the mixed solvent of methylene dichloride and heptane is obtained light green flakes crystal, be product double salicylaldehyde amine imines nickel compound 4, weighing obtains 0.92g, and productive rate is 57.5%.Ultimate analysis (is pressed C
44H
66Br
2N
6NiO
2Calculate, %), theoretical value: C, 56.85 H, 7.16, N, 9.04;
Measured value: C, 56.70 H, 7.10 N, 9.21.
1H?NMR(300MHz，DMSO-d
6，25℃)：δ9.97(2H，s，NCHN)，9.58(2H，s，CH＝N)，8.11(2H，s，Ph-H)，7.71(2H，s，Ph-H)，6.27-7.24(4H，m，NCHCHN)，4.24(4H，m，NCH
2)，3.86(6H，s，NCH
3)，3.74(4H，m，NCH
2)，?2.20(4H，m，CH
2)，0.79-1.37(36H，m，C(CH
3)
3)。
Embodiment 6: the synthetic and sign of ethylene oligomerization product
Polymerization experiment is anhydrous in strictness, carry out under the condition of anaerobic, used glassware and stirring with magneton drying in baking oven (120 ℃).The 50mL polyreaction bottle that will have gas introduction tube and magnetic stir bar vacuumizes more than the dry 1h under the infrared lamp baking continuously; Feed and fill ethene to normal pressure after ethene is replaced 2 times; The ionic liquid that is dissolved with 5 μ mol catalyzer 1 that adds 2ml.Add heptane, stir, constant temperature is at 0 ℃.Add and contain 1450 μ mol AlEt
2Cl (Al/Ni=290) n-heptane solution initiated polymerization, wherein controlling the heptane cumulative volume is 30ml.Feed ethene and write down the initial pressure of ethylene gas, the pressure of keeping in the reaction flask is 0.05MPa, and the pressure change of record ethylene gas stops to feed ethene behind the 1h.
Extract a certain amount of heptane (perhaps toluene) solution out with syringe, be driven in the sealing ampere bottle that contains 95% ethanol solution hydrochloride freezing standing demix; Extract upper organic phase out with syringe again and be driven in the sealing ampere bottle that contains a certain amount of anhydrous sodium sulphate and sodium bicarbonate, pH value to 7 is transferred in dehydration.Extract dehydration neutral organic phase out with syringe more at last, with after the filtering head filter salts of 0.20 μ m sample being expelled in the sealing ampere bottle, the gained sample is directly used in the GC-Ms test.
Calculate reaction consumes ethene quality and show that reaction TOF value is a 16400mol ethene/(molNih).The result shows that the ethylene oligomerization products distribution is:
C4(wt％)：42.3％，C6(wt％)：51.7％，C8(wt％)：4.0％，＞C8(wt％)：2.0％。
Embodiment 7: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, except temperature control changes 25 ℃ into, other condition is identical.
The TOF value is a 36400mol ethene/(molNih).
The ethylene oligomerization products distribution is: C4 (wt%): 8.0%, and C6 (wt%): 55.6%, C8 (wt%): 28.6%,＞C8 (wt%): 7.8%.
Embodiment 8: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, except temperature control changes 50 ℃ into, other condition is identical.
The TOF value is a 26800mol ethene/(mol.Ni.h).
The ethylene oligomerization products distribution is: C4 (wt%): 10.2%, and C6 (wt%): 66.1%, C8 (wt%): 19.2%,＞C8 (wt%): 4.5%.
Embodiment 9: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, except temperature control changes 75 ℃ into, other condition is identical.
The TOF value is a 4640mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 37.1%, and C6 (wt%): 51.1%, C8 (wt%): 9.9%,＞C8 (wt%): 1.9%.
Embodiment 10: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer changes 2 into, and other condition is identical.
The TOF value is a 25000mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 20.6%, and C6 (wt%): 51.3%, C8 (wt%): 23.7%,＞C8 (wt%): 4.4%.
Embodiment 11: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 2, and temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 34600mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 9.3%, and C6 (wt%): 60.5%, C8 (wt%): 24.9%,＞C8 (wt%): 5.3%.
Embodiment 12: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 2, and temperature is controlled at 50 ℃, and other condition is identical.
The TOF value is a 12100mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 14.8%, and C6 (wt%): 67.5%, C8 (wt%): 14.9%,＞C8 (wt%): 2.8%
Embodiment 13: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 3,, other condition is identical.
The TOF value is a 15400mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 20.8%, and C6 (wt%): 51.0%, C8 (wt%): 24.8%,＞C8 (wt%): 3.4%.
Embodiment 14: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 3, and temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 41800mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 5.2%, and C6 (wt%): 52.7%, C8 (wt%): 35.2%,＞C8 (wt%): 6.9%.
Embodiment 15: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 3, and temperature is controlled at 50 ℃, and other condition is identical.
The TOF value is a 32200mol ethene/(molNh).
The ethylene oligomerization products distribution is C4 (wt%): 6.9%, and C6 (wt%): 59.5%, C8 (wt%): 27.9%,＞C8 (wt%): 5.7%.
Embodiment 16: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 4, and other condition is identical.
The TOF value is a 5400mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 88.6%, and C6 (wt%), 11.4%, C8 (wt%): 0%,＞C8 (wt%): 0%.
Embodiment 17: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 4, and temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 35700mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 22.0%, and C6 (wt%): 55.3%, C8 (wt%): 20.0%,＞C8 (wt%): 2.7%.
Embodiment 18: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, catalyzer uses 4, and temperature is controlled at 50 ℃, and other condition is identical.
The TOF value is a 22500mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 17.7%, and C6 (wt%): 62.6%, C8 (wt%): 17.0%,＞C8 (wt%): 2.0%.
Embodiment 19: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, change Al/Ni=116, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 21100mol ethene/(mol.Ni.h).
The ethylene oligomerization products distribution is C4 (wt%): 18.2%, and C6 (wt%): 46.9%, C8 (wt%): 11.9%,＞C8 (wt%): 23.0%.
Embodiment 20: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, change Al/Ni=400, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is 50400mol ethene/(molNih) (catalyzer utilization for the first time).
The ethylene oligomerization products distribution is: C4 (wt%): 11.7%, and C6 (wt%): 53.0%, C8 (wt%): 29.9%,＞C8 (wt%): 5.4%.Catalyzer retention rate: 99.5%.
After reaction finished, standing demix was realized separate alternate with ionic liquid of organic phase by syringe, added again then and contained 1450 μ mol AlEt
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 36100mol ethene/(molNih) (catalyzer circulates for the second time).
The ethylene oligomerization products distribution is: C4 (wt%): 14.1%, and C6 (wt%): 49.3%, C8 (wt%): 30.6%,＞C8 (wt%): 6.0%.99.5％。Catalyzer retention rate: 99.0%.
And then, add again and contain 580 μ mol AlEt by separate alternate of syringe realization organic phase with ionic liquid
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 25700mol ethene/(molNih) (catalyzer circulates for the third time).
The ethylene oligomerization products distribution is: C4 (wt%): 16.1%, and C6 (wt%): 58.6%, C8 (wt%): 22.4%,＞C8 (wt%): 2.9%.Catalyzer retention rate: 98.1%.
Embodiment 21: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, change Al/Ni=580, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 42500mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 7.2%, and C6 (wt%): 61.6%, C8 (wt%): 26.1%,＞C8 (wt%): 5.1%.
Embodiment 22: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, change Al/Ni=870, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 22900mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 17.6%, and C6 (wt%): 66.3%, C8 (wt%): 14.4%,＞C8 (wt%): 1.7%.
Embodiment 23: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 2, change Al/Ni=400, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 49300mol ethene/(molNih), (catalyzer utilization for the first time).
The ethylene oligomerization products distribution is: C4 (wt%): 9.5%, and C6 (wt%): 58.8%, C8 (wt%): 27.4%,＞C8 (wt%): 4.3%.Catalyzer retention rate: 99.4%.
After reaction finished, standing demix was realized separate alternate with ionic liquid of organic phase by syringe, added again then and contained 1450 μ mol AlEt
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 40000mol ethene/(molNih) (catalyzer circulates for the second time).
The ethylene oligomerization products distribution is: C4 (wt%): 10.8%, and C6 (wt%): 61.0%, C8 (wt%): 24.3%,＞C8 (wt%): 3.9%.Catalyzer retention rate: 98.5%.
And then, add again and contain 580 μ mol AlEt by separate alternate of syringe realization organic phase with ionic liquid
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 21400mol ethene/(molNih) (catalyzer circulates for the third time).
The ethylene oligomerization products distribution is: C4 (wt%): 11.2%, and C6 (wt%): 61.7%, C8 (wt%): 23.5%,＞C8 (wt%): 3.6%.Catalyzer retention rate: 98.0%.
Embodiment 24: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 2, change Al/Ni=580, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 41400mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 8.4%, and C6 (wt%): 51.2%, C8 (wt%): 36.2%,＞C8 (wt%): 4.2%.
Embodiment 25: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 3, change Al/Ni=i16, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 26800mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 12.2%, and C6 (wt%): 59.0%, C8 (wt%): 20.3%,＞C8 (wt%): 8.5%.
Embodiment 26: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 3, change Al/Ni=400, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 47900mol ethene/(molNih), (catalyzer utilization for the first time).
The ethylene oligomerization products distribution is C4 (wt%): 9.6%, and C6 (wt%): 48.9%, C8 (wt%): 35.1%,＞C8 (wt%): 6.4%.Catalyzer retention rate:＞99.9%.
After reaction finished, standing demix was realized separate alternate with ionic liquid of organic phase by syringe, added again then and contained 1450 μ mol AlEt
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 40000mol ethene/(molNih) (catalyzer circulates for the second time).
The ethylene oligomerization products distribution is: C4 (wt%): 11.0%, and C6 (wt%): 54.6%, C8 (wt%): 29.0%,＞C8 (wt%): 5.4%.Catalyzer retention rate:＞99.9%.
And then, add again and contain 580 μ mol AlEt by separate alternate of syringe realization organic phase with ionic liquid
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 28600mol ethene/(molNih) (catalyzer circulates for the third time).
The ethylene oligomerization products distribution is: C4 (wt%): 26.0%, and C6 (wt%): 57.0%, C8 (wt%): 14.8%,＞C8 (wt%): 2.2%.Catalyzer retention rate:＞99.9%.
Embodiment 27: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 3, change Al/Ni=580, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 35700mol ethene/(mol.Ni.h).
The ethylene oligomerization products distribution is C4 (wt%): 5.5%, and C6 (wt%): 45.4%, C8 (wt%): 40.3%,＞C8 (wt%): 8.8%.
Embodiment 28: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 4, change Al/Ni=400, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 36800mol ethene/(molNi.h), (catalyzer utilization for the first time).
The ethylene oligomerization products distribution is C4 (wt%): 14.0%, and C6 (wt%): 54.1%, C8 (wt%): 26.9%,＞C8 (wt%): 5.0%.Catalyzer retention rate:＞99.9%.
After reaction finished, standing demix was realized separate alternate with ionic liquid of organic phase by syringe, added again then and contained 1450 μ mol AlEt
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 58600mol ethene/(molNih) (catalyzer utilization for the second time).
The ethylene oligomerization products distribution is: C4 (wt%): 13.1%, and C6 (wt%): 61.0%, C8 (wt%): 22.6%,＞C8 (wt%): 3.3%.Catalyzer retention rate:＞99.9%.
And then, add again and contain 580 μ mol AlEt by separate alternate of syringe realization organic phase with ionic liquid
2The n-heptane solution of Cl (Al/Ni=290) 30ml, behind the reaction 1h, calculating the TOF value is 21800mol ethene/(molNih) (catalyzer utilization for the third time).
The ethylene oligomerization products distribution is: C4 (wt%): 26.5%, and C6 (wt%): 61.2%, C8 (wt%): 10.8%,＞C8 (wt%): 1.5%.Catalyzer retention rate:＞99.9%.
Embodiment 29: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 4, change Al/Ni=580, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 42500mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 7.6%, and C6 (wt%): 51.0%, C8 (wt%): 34.1%,＞C8 (wt%): 7.3%.
Embodiment 30: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 4, change Al/Ni=700, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 43800mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 11.8%, and C6 (wt%): 61.5%, C8 (wt%): 23.2%,＞C8 (wt%): 3.5%.
Embodiment 31: the synthetic and sign of ethylene oligomerization product
Press the polymerization process of embodiment 6, use catalyzer 4, change Al/Ni=870, temperature is controlled at 25 ℃, and other condition is identical.
The TOF value is a 40000mol ethene/(molNih).
The ethylene oligomerization products distribution is C4 (wt%): 8.4%, and C6 (wt%): 63.8%, C8 (wt%): 23.3%,＞C8 (wt%): 4.5%
Claims (9)
1. the method for a synthesizing short-chain olefin by ethylene oligomerization, it is synthetic by the effect that loads on the catalyzer on the ionic liquid ethylene oligomerization reaction to take place down, it is characterized in that described catalyzer is made up of double salicylaldehyde imine nickel complex and aluminum alkyls, both mol ratios are 1: 100～900.
2. the method for claim 1 is characterized in that, the mol ratio of described double salicylaldehyde imine nickel complex and aluminum alkyls is 1: 400～700.
3. the method for claim 1 is characterized in that, the structural formula of described double salicylaldehyde imine nickel complex is suc as formula (I).
4. the method for claim 1 is characterized in that, described aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or ethyl aluminum dichloride.
5. the method for claim 1 is characterized in that, described ionic liquid is an imidazoles aluminic acid type, and its structural formula is
Or
N is 1 to 3, R
3And R
4Alkyl for the different chain length degree.
6. the method for claim 1 is characterized in that, the temperature of described ethylene oligomerization reaction is 0～75 ℃.
7. method as claimed in claim 6 is characterized in that, the temperature of described ethylene oligomerization reaction is 25～50 ℃.
8. the method for claim 1 is characterized in that also adding solvent.
9. method as claimed in claim 8 is characterized in that described solvent is inertia aromatic solvent, straight-chain paraffin or halohydrocarbon.
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