CN106673933A - 1-butylene dimerization method - Google Patents
1-butylene dimerization method Download PDFInfo
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- CN106673933A CN106673933A CN201510751137.5A CN201510751137A CN106673933A CN 106673933 A CN106673933 A CN 106673933A CN 201510751137 A CN201510751137 A CN 201510751137A CN 106673933 A CN106673933 A CN 106673933A
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- Prior art keywords
- butylene
- dimerization
- aluminum
- reaction
- alkyl
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- -1 phenanthroline amine cobalt complex Chemical class 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 229910052756 noble gas Inorganic materials 0.000 claims description 5
- 150000002835 noble gases Chemical class 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000006384 oligomerization reaction Methods 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- FNWCDKSFAOGZEO-UHFFFAOYSA-N 1-propan-2-ylperoxypropane Chemical compound CCCOOC(C)C FNWCDKSFAOGZEO-UHFFFAOYSA-N 0.000 description 1
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical class NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical class CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 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
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a 1-butylene dimerization method. The method is characterized in that under effects of a main catalyst of a chlorinated-2-n-propiono-1,10-phenanthroline amine cobalt (II) complex shown as a formula I and an aluminum-containing cocatalyst as well as existence of an organic solvent, 1-butylene is subjected to a dimerization reaction. In the formula (I), R1, R2, R3, R4 and R5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl groups, halogen, C1-C6 alkoxy groups and a nitro group. The novel phenanthroline amine cobalt complex as the main catalyst of the 1-butylene dimerization initiates novel field of a butylene dimer catalyst, the reaction process initiation is rapid, operation is stable, repeatability is good, high raw material conversion rate, reaction activity and product linear rate can be obtained, and the method provides good reaction effect and economic benefit for octylene preparation by 1-butylene dimerization.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of 1-butylene process for dimerization.
Background technology
Octene is important Organic Ingredientss and chemical intermediate, can be used as plasticizer, detergent and lubricating oil
Raw material.Polyethylene (PE) of the 1- octenes mainly for the production of high-quality, especially production of linear Low Density Polyethylene
(LLDPE) comonomer.2- octenes and other linear octenes can also generate octene with synthetic detergent
Aldehyde or octene ester, as essence, the raw material of spice and other medicine intermediates.
At present, the production method of octene mainly has wax destructive distillation method, ethylene oligomerization method, fatty alcohol dehydriding etc..
In the research of preparing alpha-olefin by ethane oligomerisation, the 1- octenes of only 10%-19% are generated, and are existed substantial portion of
1-butylene by-product, the chemical utilization rate of this part butylene are very low, burn mostly as fuel, extremely waste.
Therefore, it is particularly important the 1-butylene of excessive, low value to be converted into the linear octene of high added value.
The catalyst of butene oligomerization mainly has Ziegler type homogeneous catalysts (such as nickel complex catalyst) and multiphase
Catalyst is (as solid phosphoric acid catalyst, zeolite molecular sieve catalyst, loaded catalyst and nickeliferous multiphase are urged
Agent etc.).In recent years, the efficient catalyst system and catalyzing based on ionic liquid and related process are developed again.At present,
Also having been reported that is used to be catalyzed the dimerization reaction of 1-butylene by pyridine radicals cobalt (II) complex, and obtains good fourth
Alkene conversion ratio and the linear rate of octene.It remains desirable, however, that the method for developing other butene dimerizations, more to optimize
Process conditions 1-butylene is converted into into linear octene, meet the market demand to linear octene.
The content of the invention
It is an object of the invention to provide a kind of new method for 1-butylene dimerization, to prepare high selectivity
C8 products.The method adopts new catalyst system, makes 1-butylene occur two under certain reaction condition
Poly- reaction.In the method, it is possible to obtain higher catalyst activity, 1-butylene conversion ratio and octene is linear
Rate also increases, and is especially obtained in that extremely high Octenes selectivity, and be swift in response, operate steadily,
It is reproducible.
According to the present invention, there is provided a kind of 1-butylene process for dimerization, methods described are included 1-butylene in such as Formulas I
The major catalyst and co-catalysis containing aluminum of positive propiono -1,10- phenanthroline condensed amines cobalt (II) coordination compounds of shown chlorination 2-
In the presence of agent, and dimerization reaction is carried out in presence of organic solvent,
Wherein, R1、R2、R3、R4And R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6
Alkoxyl and nitro.That is, R1、R2、R3、R4And R5It is each independently any one in above-mentioned group.
By the method described in present invention offer for 1-butylene dimerization, it is possible to obtain the C8 of high selectivity is produced
Thing.Therefore, from for still further aspect, the invention provides a kind of preparation method of C8 hydrocarbon compounds.
Even it is also understood that being, the invention provides as the caltalyst used in the inventive method ties up to 1-butylene two
Application in the preparation of poly- or C8 hydrocarbon compounds.
It has been found by the inventor that the three tooth nitrogen of phenanthroline shown in formula I provided according to the present invention
The coordination compound of structure has very high catalysis activity to the reaction of butylene homogeneous polymerization, particularly with butene dimerization product
With very high selectivity.There is 1,10- phenanthroline condensed amine irons coordination compound in prior art for ethylene oligomerization
Catalyst, higher catalysis activity can be produced, and the linear rate of oligomerization product is higher.But, at these
In reaction, the molecular weight of product that ethylene oligomerization is obtained is distributed more widely, and the selectivity of C8 products is simultaneously not high enough to.And
It is an object of the invention to provide the 1-butylene process for dimerization of high selectivity, other side reactions that will be beyond dimerization
Minimize, to obtain high yield octene.Additionally, for ethylene oligomerization and the reaction of two class of butene dimerization,
The difference of raw material can cause the difference of reaction mechanism, ethylene to make raw material, main generation ethylene oligomerization reaction, and 1-
Butylene makees raw material, then preferentially carry out dimerization reaction.This be due to 1-butylene it is sterically hindered due to, be unfavorable for
The multistep reaction of alkene and there is chain propagation reaction.The present inventor is adopted shown in formula I pioneeringly
The cobalt complex of three tooth N structure of phenanthroline not only obtains higher catalysis as butene dimerization catalytic component
Agent activity, and generate abnormal high butene dimerization selectivity.
By the method described in present invention offer for 1-butylene dimerization, it is possible to obtain the C8 of high selectivity is produced
Thing.Therefore, from for still further aspect, the invention provides a kind of preparation method of C8 hydrocarbon compounds.
Even it is also understood that being, the invention provides as the caltalyst used in the inventive method ties up to 1-butylene two
Application in the preparation of poly- or C8 hydrocarbon compounds.As the product of the inventive method is mainly octene, therefore this
It is bright to essentially provide a kind of method for preparing octene.
In the present invention, term " C1-C6Alkyl " refers to the saturated straight chain containing 1-6 carbon atom or side chain
Alkyl.As C1-C6Alkyl, it can be mentioned that methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl
Base, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl.The present invention's
In method, the C1-C6Alkyl is preferably methyl, ethyl, n-pro-pyl or isopropyl.
In the present invention, term " C1-C6Alkoxyl " refers to above-mentioned C1-C6Alkyl is connected with an oxygen atom
The group for obtaining.As C1-C6Alkoxyl, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen
Base, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, just own oxygen
Base and secondary hexyloxy.In the method for the invention, the C1-C6Alkoxyl is particularly preferably methoxyl group or ethoxy
Base.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine.It is in the method for invention, described
Halogen is particularly preferably fluorine, chlorine or bromine.
In the certain preferred embodiments of the present invention, R1、R2、R3、R4And R5Be each independently selected from hydrogen,
Methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.
In a further preferred embodiment, R1And R5For ethyl, and R2、R3And R4It is hydrogen.
In the present invention, aikyiaiurnirsoxan beta or alkyl aluminum compound, and preferably alumina can be selected from containing aluminum cocatalyst
Alkane.
In the present invention, aikyiaiurnirsoxan beta is preferably C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is straight chain or props up
The C of chain1-C4Alkyl.Also, in the method for the invention, the aikyiaiurnirsoxan beta is preferably MAO, changes
At least one in property MAO, ethylaluminoxane and isobutyl aluminium alkoxide, more preferably modified methyl alumina
Alkane.It is known that trimethyl aluminium obtains MAO with water reaction.Preferably used by adding in the present invention
Enter a small amount of triisobutyl aluminium, part methyl is replaced and obtained modified methylaluminoxane by isobutyl group, which is more
Be conducive to forming metal alkyl cation with metallic catalyst, so as to be conducive to catalyzing butene dimerization reaction.
In the present invention, it is preferred to alkyl aluminum compound has formula AlRnXm, integers of the wherein n for 1-3, m
For the integer of 0-2, and m+n is equal to 3；N R is each independently selected from straight or branched C1-C8Alkyl；m
Individual X is each independently selected from halogen, is preferably selected from chlorine and bromine.That is, when n be 2 or 3 when, 2 or
3 R are each independently selected from straight or branched C1-C8Alkyl；When n is 2,2 X are independently of one another
Selected from halogen.Also, in the method for the invention, the alkyl aluminum compound is preferably trimethyl aluminium, three second
Base aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and dichloro
Change at least one in aluminium ethide, more preferably triethyl aluminum.
In the method for the invention, organic solvent be preferably benzene,toluene,xylene, chlorobenzene, bromobenzene, just oneself
Alkane, hexamethylene, hexahydrotoluene, heptane, dichloromethane and C6-C16Alhpa olefin at least one, more
It is preferred that hexamethylene.
In the certain preferred embodiments of the present invention, major catalyst with the mass ratio of 1-butylene is
0.83×10-4-2×10-4, also preferably 0.83 × 10-4-1.6×10-4, more preferably 0.9 × 10-4-1.5×10-4,
Most preferably 1 × 10-4。
In the certain preferred embodiments of the present invention, the cobalt in aluminum in promoter and major catalyst mole
Than for (50-1000):1, preferably (100-800):1, more preferably (100-500):1, further preferably
For (150-390):1.
In the 1-butylene process for dimerization of the present invention, the temperature of dimerization reaction is 10-100 DEG C, preferably 10-80 DEG C,
More preferably 20-50 DEG C, further preferred 30-40 DEG C；The dimerization reaction time is 2-16h, preferred 3-6h；Two
The pressure of poly- reaction is more than 0.4MPa, such as 0.4-5MPa.
In a specific embodiment of the method that the present invention is provided, the method for 1-butylene dimerization includes following step
Suddenly：(1) operation such as high temperature drying, vacuum displacement is carried out to reaction system, it is ensured that anhydrous and oxygen-free in system；
(2) line replacement is entered to reaction system using nitrogen；(3) a certain amount of organic solvent is added, is sufficiently stirred for；
(4), after adding major catalyst and promoter, under a certain pressure a certain amount of 1-butylene is pressed into nitrogen
Reactor starts reaction；(5) holding reaction pressure is more than 0.4MPa to guarantee 1-butylene as liquid, and instead
Temperature is answered for 2～16h is reacted at 10～100 DEG C；(6), after stopped reaction, take product and first wash and use afterwards
Gas chromatogram (GC) is analyzed.
The invention provides a kind of method for 1-butylene dimerization, comprises the following steps：It is filled with reactor
Noble gases, are subsequently adding organic solvent, major catalyst and promoter, are pressed into 1-butylene with noble gases
Reacted in reactor；Wherein, the organic solvent be hexamethylene, dichloromethane, benzene and toluene in extremely
Few one kind；The major catalyst has such as formula I above structural formula, wherein, R1And R5For ethyl, and R2、R3
And R4It is hydrogen；The promoter is modified methylaluminoxane and/or triethyl aluminum；In the promoter
Aluminum and the major catalyst in the mol ratio of cobalt be (100-400):1；Reaction pressure is 0.4-5MPa, instead
Temperature is answered for 20-50 DEG C, the response time is 3-6h.The noble gases are preferably nitrogen.
In the present invention, major catalyst and promoter can add reaction system after first being dissolved with organic solvent
In.
The method provided using the present invention makes 1-butylene carry out dimerization reaction, and the product of acquisition is mainly C8And C12,
Wherein C8Selectivity can reach more than 99.8%, and the only C of trace12；And C8Linear rate exist
More than 96%；The conversion ratio of 1-butylene can reach more than 45%；The oligomerization activity of catalyst is up to 4500g bis-
It is more than polymers/gCo coordination compounds.
Relative to prior art, present invention uses new phenanthroline cobalt complex is anti-as 1-butylene dimerization
The major catalyst answered, has not only started the frontier of butene dimerization catalyst, and reaction process cause it is rapid,
Stable, the linear rate of feed stock conversion, reactivity and product all increases, and is especially that of obtaining very
High dimer selectivity, and reaction cost also preferably balanced, it is practical.Therefore, the present invention
The method of offer enables 1-butylene to be effectively utilised, and has both considered catalytic effect, has taken into account economic effect again
Benefit, with wide industrial applications prospect.
Specific embodiment
The present invention will be described further by specific embodiment below, it should be appreciated that the scope of the present invention
It is not limited to this.
Embodiment 1
With positive propiono -1 of chlorination 2-, it is major catalyst that 10- phenanthroline 2,6- of contracting diethylanilines close cobalt (II), by 1-
Butylene carries out dimerization reaction, specifically includes following steps：(1) high temperature is carried out to 300ml stainless steel cauldrons
Drying, vacuum displacement etc. are operated, it is ensured that anhydrous and oxygen-free in system；(2) reactor is put using nitrogen
Change；(3) 10ml hexamethylene is added in a kettle., be sufficiently stirred for；(4) 2.75ml modified methyls are added
Aikyiaiurnirsoxan beta n-heptane solution (concentration is 1.8796mol/L), adds positive propiono -1 of 5ml chlorination 2-, the contracting of 10- phenanthroline
2,6- diethylanilines close cobalt (II) (molecular weight：496) cyclohexane solution (concentration is 1mg/ml), makes system
Al/Co=500 (mol ratio)；(5) 50g 1-butylene is pressed in reactor with nitrogen, pressure is maintained at 0.4Mpa
Above to guarantee 1-butylene as liquid；(6) 3h is reacted in the case where reaction temperature is for 30 DEG C；(7) stopped reaction,
A small amount of product is taken out after cooling, with 5% dilute hydrochloric acid and laggard circulation of qi promoting analysis of hplc.As a result：1-
Butene conversion is 36.02%, and catalyst activity is 3600g dimers/g Co coordination compounds, and product contains C8
99.92wt%, C120.08%, wherein linear C897%.Concrete analysis the results are shown in Table 1.
Embodiment 2
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Al/Co=200 (mol ratio),
Reaction temperature is 40 DEG C, and analysis result is shown in Table 1.
Embodiment 3
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Al/Co=100 (mol ratio),
Analysis result is shown in Table 1.
Embodiment 4
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Major catalyst consumption is 4.5mg,
Al/Co=390 (mol ratio), reaction temperature are changed into 20 DEG C, and the response time is 6 hours, and analysis result is shown in Table
1。
Embodiment 5
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Al/Co=200 (mol ratio),
Response time is changed into 15h, and analysis result is shown in Table 1.
Embodiment 6
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Urged to help using triethyl aluminum
Agent, Al/Co=200 (mol ratio), analysis result is shown in Table 1.
Embodiment 7
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Using 7mg chlorination 2- positive third
Acyl group -1,10- phenanthroline contracting 2,6- dichloroanilines close cobalt (II) (molecular weight：508) it is major catalyst, Al/Co=200
(mol ratio), analysis result is shown in Table 1.
Embodiment 8
1-butylene dimerization reaction is carried out using the method for embodiment 1, difference is：Using 7mg chlorination 2- positive third
Acyl group -1, it is major catalyst that 10- phenanthroline contracting 4- butoxy -3- nitro-analines close cobalt (II), Al/Co=200 (mole
Than), analysis result is shown in Table 1.
Table 1
From table 1 it follows that the method provided according to the present invention carries out 1-butylene dimerization reaction, with higher
Reactivity and 1-butylene conversion ratio, especially with very high dimerization reaction selectivity, in polymerizate
Dimer content more than 99.8%, correspondingly, the selectivity of C8 hydrocarbon compounds all more than 99.8%, line
Property rate also can reach 97%.
Although the present invention is described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side of present invention record, difference
The each several part of specific embodiment and the various features enumerated can be combined or all or part of exchange.Above-mentioned
Each specific embodiment in, those with reference to another embodiment embodiment can suitably with its
Its embodiment is combined, and this is will be to understand by those skilled in the art.Additionally, those skilled in the art
It will be understood that, description above is only the mode of example, it is no intended to limit the present invention.
Claims (10)
1. a kind of 1-butylene process for dimerization, methods described include by 1-butylene in chlorination 2- shown in formula I just
Propiono -1, the major catalyst of 10- phenanthroline condensed amine cobalt (II) coordination compounds and containing in the presence of aluminum cocatalyst, with
And carry out dimerization reaction in presence of organic solvent,
Wherein, R1、R2、R3、R4And R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6
Alkoxyl and nitro.
2. method according to claim 1, it is characterised in that R1、R2、R3、R4And R5Each solely
Hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitre are selected from the spot
Base；It is preferred that R1And R5For ethyl, and R2、R3And R4It is hydrogen.
3. method according to claim 1 and 2, it is characterised in that described to be selected from aluminum containing aluminum cocatalyst
Oxygen alkane or alkyl aluminum compound, preferred aikyiaiurnirsoxan beta.
4. method according to claim 3, it is characterised in that the aikyiaiurnirsoxan beta is C1-C4Alkyl alumina
Alkane, wherein C1-C4Alkyl of the alkyl for straight or branched；It is preferred that the aikyiaiurnirsoxan beta is MAO, is modified
At least one in MAO, ethylaluminoxane and isobutyl aluminium alkoxide.
5. the method according to claim 3 or 4, it is characterised in that the formula of the alkyl aluminum compound
For AlRnXm, integers of the wherein n for 1-3, integers of the m for 0-2, and m+n is equal to 3；N R is each
Independently selected from straight or branched C1-C8Alkyl；M X is each independently selected from halogen；Also, the alkane
Base aluminium compound be preferably trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum,
At least one in tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride.
6. the method according to any one in claim 1-5, it is characterised in that the organic solvent choosing
From benzene,toluene,xylene, chlorobenzene, bromobenzene, normal hexane, hexamethylene, hexahydrotoluene, heptane, dichloro
Methane and C6-C16Alhpa olefin at least one.
7. the method according to any one in claim 1-6, it is characterised in that the major catalyst with
The mass ratio of 1-butylene is 0.83 × 10-4-2×10-4, preferably 0.9 × 10-4-1.5×10-4。
8. the method according to any one in claim 1-7, it is characterised in that in the promoter
Aluminum and the major catalyst in the mol ratio of cobalt be (50-1000):1, preferably (100-500):1, further
It is preferred that (150-390):1.
9. the method according to any one in claim 1-8, it is characterised in that the temperature of dimerization reaction
For 0-100 DEG C, preferably 20-50 DEG C；The time of dimerization reaction is 2-16h, preferred 3-6h；Dimerization reaction
Pressure is 0.4-5MPa.
10. a kind of 1-butylene process for dimerization, comprises the following steps：Noble gases are filled with reactor, then
Organic solvent, major catalyst and promoter are added, 1-butylene is pressed in reactor with noble gases is carried out instead
Should,
Wherein,
The organic solvent is at least one in hexamethylene, Pentamethylene., hexahydrotoluene and heptane；
The major catalyst has such as following formula I structural formula：
Wherein, R1And R5For ethyl, and R2、R3And R4It is hydrogen；
The promoter is modified methylaluminoxane；
The mol ratio of the cobalt in the aluminum in the promoter and the major catalyst is (100-400):1；
Reaction pressure is 0.4-5MPa, and reaction temperature is 20-50 DEG C, and the response time is 3-6h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386819A (en) * | 2002-07-15 | 2002-12-25 | 无锡复菁绿化工程科技有限公司 | Efficient drought-resistant moisture-preserving soil capable of making seedling stronger |
| CN102432414A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low temperature ethylene oligomerization method |
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2015
- 2015-11-06 CN CN201510751137.5A patent/CN106673933A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386819A (en) * | 2002-07-15 | 2002-12-25 | 无锡复菁绿化工程科技有限公司 | Efficient drought-resistant moisture-preserving soil capable of making seedling stronger |
| CN102432414A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low temperature ethylene oligomerization method |
Non-Patent Citations (1)
| Title |
|---|
| BROOKE L. SMALL ET AL.: "Comparative Dimerization of 1-Butene with a Variety of Metal Catalysts, and the Investigation of a New Catalyst for C-H Bond Activation", 《CHEM. EUR. J.》 * |
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