CN116037207A - Catalyst composition for olefin oligomerization and preparation method and application thereof - Google Patents
Catalyst composition for olefin oligomerization and preparation method and application thereof Download PDFInfo
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- CN116037207A CN116037207A CN202111266432.3A CN202111266432A CN116037207A CN 116037207 A CN116037207 A CN 116037207A CN 202111266432 A CN202111266432 A CN 202111266432A CN 116037207 A CN116037207 A CN 116037207A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 39
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 53
- -1 alkyl aluminum compound Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005977 Ethylene Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- 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
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 46
- 238000004817 gas chromatography Methods 0.000 description 38
- 238000004458 analytical method Methods 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LSBMZQYNOULOIA-UHFFFAOYSA-N cyclohexane triethylalumane Chemical compound C1CCCCC1.C(C)[Al](CC)CC LSBMZQYNOULOIA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000630 rising effect 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
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil 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
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst composition for olefin oligomerization, comprising: a main catalyst represented by the formula (I), an alkyl aluminum compound, cyclohexane and water,
in the formula (I), R 1 ‑R 11 The same or different are each independently selected from hydrogen, C 1 ‑C 6 Alkyl, halogen, C 1 ‑C 6 Alkoxy and nitro; m is Fe (II), co (II) or Ni (II). The invention takes the alkyl aluminum compound as the auxiliary agent and cyclohexane as the solvent, and simultaneously adds the water with specific content, thereby effectively improving the activity of the catalyst composition and reducing the undesirable C 4 The yield of the product is increased at the same time as the expected C 6 ～C 10 、C 6 ～C 18 、C 6 ～C 18 The yield of the linear alpha-olefin product and the ethylene oligomerization reaction can be carried out under the condition of higher temperature which is easy to realize and operate, thereby greatly reducing the energy consumption.
Description
Technical Field
The invention relates to the technical field of olefin oligomerization, in particular to a catalyst composition for olefin oligomerization, a preparation method and application thereof.
Background
The linear alpha-olefin has wide application in the fields of ethylene comonomer, surfactant synthetic intermediate, alcohol for plasticizer, synthetic lubricating oil, oil additives and the like. In recent years, with the continued development of the polyolefin industry, the worldwide demand for α -olefins has grown rapidly.
The vast majority of alpha-olefins are currently produced by ethylene oligomerization. Catalysts used in the ethylene oligomerization process are mainly nickel-based, chromium-based, zirconium-based, aluminum-based, etc., and in recent years, the Brookhart group (Brookhart, M et al, J.am.chem.Soc.,1998,120,7143-7144; WO99/02472,1999), the Gibson group (Gibson, V.C.et al, chem.Commun.,1998,849-850; chem.Eur.J.,2000, 2221-2231) have found that tridentate pyridine imine complexes of Fe (II) and Co (II), respectively, catalyze ethylene oligomerization with very high catalytic activity and also very high selectivity for alpha-olefins.
The group Sun Wenhua of the institute of chemistry of China reports a catalyst for oligomerization of ethylene (Organometallics 2006,25,666-677) which is 2-acetyl-1, 10-phenanthroline-2, 6-dimethylaniline iron (II) chloride in the presence of Methylaluminoxane (MAO) as a cocatalyst or in the presence of a modified catalystUnder the action of methylaluminoxane (MMAO), when the mole ratio of metal aluminium in cocatalyst and central metal in main catalyst is 1000, the oligomerization and polymerization activity can be up to 3.9X10 at 40 deg.C 7 g·mol(Fe) -1 ·h -1 And, as the reaction temperature further increases, both the activity and the distribution coefficient decrease. However, both MAO and MMAO are used as cocatalysts, which are expensive and excessive in dosage, and the use of the cocatalysts in the oligomerization of ethylene in a large scale tends to result in high production costs.
In addition, in China patent (CN 1850339A), an attempt was made to use a low-cost cocatalyst comprising 2-acetyl-1, 10-phenanthroline-2, 6-diethylaniline iron (II) chloride as a main catalyst, wherein the catalyst activity was only 2.7X10 when triethylaluminum was used as the cocatalyst 5 g·mol(Fe) -1 ·h -1 The industrial requirements cannot be met; meanwhile, at the reaction temperature below 40 ℃, chilled water is generally required to be used as a reaction condensing medium, a refrigerating unit is required to be provided for refrigeration, and the process energy consumption is increased.
Disclosure of Invention
In view of the above problems of the prior art, an object of the present invention is to provide a catalyst composition for olefin oligomerization having a high catalytic activity and capable of reducing undesirable C 4 The yield of the product is increased at the same time as the expected C 6 ～C 10 、C 6 ～C 18 、C 6 ～C 18 Yield of linear alpha-olefin product; more importantly, the catalyst composition provided by the invention enables olefin oligomerization, especially ethylene oligomerization, to be carried out at a higher temperature (for example, 60-90 ℃) which is easy to realize and operate, so that the ethylene oligomerization under participation of the catalyst composition can take condensed water as a cooling medium, and the energy consumption is greatly reduced.
It is another object of the present invention to provide a method for producing a catalyst composition corresponding to one of the objects.
It is a further object of the present invention to provide the use of a catalyst composition corresponding to the above object.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
a catalyst composition for oligomerization of olefins comprising: a main catalyst represented by the formula (I), an alkyl aluminum compound, cyclohexane and water,
in the formula (I), R 1 -R 11 The same or different, each independently and independently selected from hydrogen, C 1 -C 6 Alkyl, halogen, C 1 -C 6 Alkoxy and nitro; m is Fe (II), co (II) or Ni (II).
In the prior art, aromatic organic solvents such as toluene or costly alkane organic solvents such as heptane are commonly used in catalyst compositions for olefin oligomerization, especially ethylene oligomerization. However, the inventors of the present application have found in the study that the use of cyclohexane as a solvent, together with an alkylaluminum compound in combination with a specific amount of water, can effectively increase the activity of the catalyst composition and reduce the undesirable C 4 Yield of the product while increasing the desired C 6 ～C 10 、C 6 ～C 18 、C 6 ～C 18 Yield of linear alpha-olefin product. More importantly, the catalyst composition provided by the invention enables the ethylene oligomerization reaction to be carried out under the condition of higher temperature which is easy to realize and operate, so that the ethylene oligomerization reaction in the presence of the catalyst composition provided by the invention can take condensed water as a cooling medium, and the energy consumption is reduced. In addition, the ethylene oligomerization reaction in the presence of the catalyst composition of the invention is initiated rapidly, runs stably and has good repeatability.
In the present invention, the term "C 1 -C 6 Alkyl "refers to a saturated straight or branched hydrocarbon group containing 1 to 6 carbon atoms. As C 1 -C 6 Alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,Isoamyl, sec-amyl, n-hexyl and sec-hexyl; methyl, ethyl, n-propyl and isopropyl are particularly preferred.
In the present invention, the term "C 1 -C 6 Alkoxy "refers to C as described above 1 -C 6 And a group obtained by linking an alkyl group to an oxygen atom. As C 1 -C 6 Alkoxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, n-hexoxy and Zhong Ji oxy groups may be mentioned; methoxy and ethoxy are particularly preferred.
In the present invention, the term "halogen" means fluorine, chlorine, bromine and iodine, and fluorine, chlorine and bromine are particularly preferred.
In some preferred embodiments of the invention, in formula (I), R 1 -R 11 Identical or different, each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy and nitro, preferably R 1 -R 6 Is hydrogen, R 7 And R is 11 Is methyl, R 8 -R 10 Is hydrogen; m is Fe (II).
In some preferred embodiments of the present invention, the weight content of the water in the catalyst composition is 100ppm to 500ppm, preferably 210ppm to 250ppm, more preferably 210ppm to 240ppm, still more preferably 210ppm to 230ppm, still more preferably 220ppm to 230ppm, based on the total weight of the cyclohexane.
The inventors of the present application have found in the study that, under the specific system of the present invention, the water content is favorable to obtain higher catalytic activity and target product yield within the above specific ranges.
The water content of the cyclohexane products used industrially according to the invention is generally from 0 to 20ppm. The cyclohexane used in the present invention is anhydrous cyclohexane. The water content defined in the present invention is achieved by additionally introducing a certain amount of water.
In some preferred embodiments of the present invention, the content of the main catalyst in the catalyst composition is 1. Mu. Mol/L to 500. Mu. Mol/L, preferably 10. Mu. Mol/L to 300. Mu. Mol/L, more preferably 10. Mu. Mol/L to 100. Mu. Mol/L, based on the total volume of the cyclohexane.
In some preferred embodiments of the invention, the molar ratio of aluminum in the alkyl aluminum compound to M in the procatalyst is greater than 30:1 and less than 900:1, preferably from 100:1 to 700:1, more preferably from 148:1 to 196:1.
In some preferred embodiments of the present invention, the alkyl aluminum compound has the formula AlR n X m Wherein R is each independently a straight or branched chain C 1 -C 8 An alkyl group; x is halogen, preferably chlorine or bromine; n is an integer from 1 to 3, m is an integer from 0 to 2, and m+n is equal to 3.
In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride; triethylaluminum is more preferred.
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
a method of preparing the catalyst composition of any of the above embodiments, comprising:
the catalyst composition is prepared by mixing the procatalyst, the aluminum alkyl compound, the cyclohexane and the water.
In some preferred embodiments of the present invention, the method for preparing the catalyst composition described above comprises: the catalyst composition is prepared by mixing an aqueous cyclohexane solution, a cyclohexane solution containing the procatalyst, and a cyclohexane solution containing the alkylaluminum compound.
In some preferred embodiments of the invention, the preparation method comprises the steps of:
1) Mixing water and cyclohexane to prepare an aqueous cyclohexane solution;
2) Adding a cyclohexane solution containing the procatalyst to the aqueous cyclohexane solution;
3) Adding a cyclohexane solution containing the alkyl aluminum compound to the solution obtained in the step 2) to obtain the catalyst composition.
In some preferred embodiments of the present invention, the concentration of the main catalyst in the cyclohexane solution containing the main catalyst is 0.1. Mu. Mol/mL to 50. Mu. Mol/mL, preferably 1. Mu. Mol/mL to 10. Mu. Mol/mL; and/or the concentration of the alkyl aluminum compound in the cyclohexane solution containing the alkyl aluminum compound is 100 mu mol/mL-1500 mu mol/mL, preferably 500 mu mol/mL-1000 mu mol/mL.
In some preferred embodiments of the present invention, the volume ratio of the aqueous cyclohexane solution, the cyclohexane solution containing the main catalyst, and the cyclohexane solution containing the aluminum alkyl compound is (80 to 99): (0.5 to 10), preferably (80 to 98): (1 to 10), more preferably (90 to 98): (1 to 5).
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
the use of the above-described catalyst composition or of a catalyst composition prepared according to the above-described preparation method in the field of olefin oligomerization, in particular in the field of ethylene oligomerization.
In some preferred embodiments of the invention, the conditions of the application include: the temperature is 10 to 90 ℃, preferably 40 to 75 ℃, more preferably 50 to 70 ℃, still more preferably 55 to 70 ℃.
In the prior art, the ethylene oligomerization reaction is usually carried out within the temperature range of 30-40 ℃, but the temperature range of 30-40 ℃ is not well realized, and the industrial operation difficulty is high. The invention can be applied in a higher and better realized temperature range, and reduces the operation difficulty in industry. Meanwhile, due to the fact that the required temperature is high, condensed water can be used as a reaction heat removal medium, compared with chilled water which is needed for achieving low reaction temperature, energy consumption is reduced, and industrial application value is obviously improved.
In some preferred embodiments of the invention, the conditions of the application include: condensed water is used as a reaction heat removal medium.
The beneficial effects of the invention are at least the following aspects:
the catalyst composition of the invention has a molar ratio of aluminum metal in the cocatalyst to central metal in the main catalyst of 196 and oligomerization and polymerization activities of up to 3.66×10 at 40 DEG C 7 g·mol(Fe) -1 ·h -1 And, as the reaction temperature further increases, the activity does not significantly decrease.
Secondly, the catalyst composition of the invention is adopted to carry out oligomerization reaction of ethylene, and the distribution coefficient of the obtained ethylene oligomerization product is more than 0.55 and even can reach 0.72.
Thirdly, the catalyst composition of the invention is adopted to carry out oligomerization of ethylene, and the obtained ethylene oligomerization product contains undesirable C 4 The yield of the product is low, while the desired C 6 ～C 10 、C 6 ～C 18 、C 6 ～C 18 The yield of linear alpha-olefin products is higher.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
In the present invention, the product distribution coefficient (k) =ethylene oligomerization chain growth rate/(chain growth rate+chain transfer rate) =c 2n+2 /C 2n 。
In the present invention, the cyclohexane solvents used are all anhydrous cyclohexane.
Example 1
(1) The reaction kettle is replaced through operations such as high-temperature drying, vacuum replacement and the like, so that no water and no oxygen are ensured in the reaction kettle;
(2) Using ethylene to replace the reaction kettle, so that the reaction system is in an ethylene environment;
(3) Adding water and a cyclohexane solvent into a reaction kettle, adding 1.37mL of triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715 mu mol/mL), adding 2mL of cyclohexane solution of 2-formyl-1, 10-phenanthroline-2, 6-dimethylaniline iron (II) chloride complex (the concentration of 2.5 mu mol/mL of 2-formyl-1, 10-phenanthroline-2, 6-dimethylaniline iron (II) chloride complex), and introducing ethylene to start oligomerization after full stirring, wherein the weight content of water is 225ppm and the Al/Fe (molar ratio) =196 based on the weight of cyclohexane;
(4) Maintaining the ethylene pressure at 1MPa and the reaction temperature at 60 ℃ for 30 minutes;
(5) The reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 2
The difference from example 1 was only that "the weight content of water was 100ppm based on the weight of cyclohexane".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 3
The difference from example 1 was only that "the weight content of water was 150ppm based on the weight of cyclohexane".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 4
The difference from example 1 was only that "the weight content of water was 300ppm based on the weight of cyclohexane".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 5
The difference from example 1 was only that "the weight content of water was 500ppm based on the weight of cyclohexane".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 6
The "2-formyl-1, 10-phenanthroline-2, 6-dimethylaniline iron (II) chloride complex" in example 1 was replaced with the "2-formyl-1, 10-phenanthroline-2, 6-dimethylaniline iron (II) chloride complex".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 7
The difference from example 1 is only that "the reaction temperature is 10 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 8
The difference from example 1 is only that "the reaction temperature is 30 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 9
The difference from example 1 is only that "the reaction temperature is 40 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 10
The difference from example 1 is only that "the reaction temperature is 50 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 11
The difference from example 1 is only that "the reaction temperature was 55 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 12
The difference from example 1 is only that "the reaction temperature was 70 ℃".
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Example 13
The difference from example 1 is only that "the reaction temperature is 80 ℃.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 1
"toluene" was used instead of "cyclohexane" in example 1.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 2
"xylene" was used instead of "cyclohexane" in example 1.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 3
"ethanol" was used instead of "cyclohexane" in example 1.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 4
"methylcyclohexane" was used instead of "cyclohexane" in example 1.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 5
"methylaluminoxane" was used instead of "triethylaluminum" in example 1.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
Comparative example 6
"triethylaluminum" in example 1 was replaced with "methylaluminoxane" and Al/Fe (molar ratio) was adjusted to 1000.
After the reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the specific analysis results are shown in table 1.
TABLE 1
Note that: in the above table, k refers to the product distribution coefficient.
As can be seen from the data in table 1 above,
firstly, the catalyst composition provided by the invention has high oligomerization activity, and when ethylene is subjected to ethylene oligomerization in the presence of the catalyst composition provided by the invention, the oligomerization can be initiated rapidly;
secondly, undesired C in the oligomerization product 4 The content of impurities is less, the distribution coefficient of the product is higher, and the reaction system initiated by the catalyst composition provided by the invention is stable in operation and good in repeatability;
thirdly, the catalyst composition provided by the invention can react at a higher reaction temperature which is easier to realize than a reaction temperature of 30-50 ℃ which is commonly adopted in the field, and condensed water can be adopted as a reaction heat removal medium, so that the energy consumption is reduced compared with chilled water which is required to be used as the reaction heat removal medium when the reaction temperature of 30-50 ℃ is adopted, and the industrial application value is obviously improved;
fourth, with the rising of the reaction temperature, the catalyst composition provided by the invention still keeps very high activity, and the distribution coefficient of the product still can reach about 0.7 without obvious drop at a higher temperature of 60-70 ℃.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A catalyst composition for oligomerization of olefins comprising: a main catalyst represented by the formula (I), an alkyl aluminum compound, cyclohexane and water,
in the formula (I), R 1 -R 11 The same or different are each independently selected from hydrogen, C 1 -C 6 Alkyl, halogen, C 1 -C 6 Alkoxy and nitro; m is Fe (II), co (II) or Ni (II), preferably R 1 -R 11 Identical or different, each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy and nitro, more preferably R 1 -R 6 Is hydrogen, R 7 And R is 11 Is methyl, R 8 -R 10 Is hydrogen; m is Fe (II).
2. The catalyst composition according to claim 1, wherein the weight content of water in the catalyst composition is 100ppm to 500ppm, preferably 210ppm to 240ppm, more preferably 210ppm to 230ppm, still more preferably 220ppm to 230ppm, based on the total weight of the cyclohexane.
3. Catalyst composition according to claim 1 or 2, characterized in that the content of the main catalyst in the catalyst composition is 1 to 500 μmol/L, preferably 10 to 300 μmol/L, more preferably 10 to 100 μmol/L, calculated on the total volume of the cyclohexane.
4. A catalyst composition according to any of claims 1-3, characterized in that the molar ratio of aluminium in the alkyl aluminium compound to M in the main catalyst in the catalyst composition is above 30:1 and below 900:1, preferably from 100:1 to 700:1, more preferably from 148:1 to 196:1.
5. The catalyst composition of any of claims 1-4, wherein the alkyl aluminum compound has the formula AlR n X m Wherein R is each independently C 1 -C 8 Straight chain alkyl or C 3 -C 8 Branched alkyl; x is halogen, preferably chlorine or bromine; n is an integer from 1 to 3, m is an integer from 0 to 2, and m+n is equal to 3; preferably, the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride; triethylaluminum is more preferred.
6. A method of preparing the catalyst composition of any one of claims 1-5, comprising:
mixing the main catalyst, the alkyl aluminum compound, the cyclohexane and the water to prepare the catalyst composition,
preferably, the catalyst composition is prepared by mixing an aqueous cyclohexane solution, a cyclohexane solution containing the main catalyst, and a cyclohexane solution containing the alkylaluminum compound,
more preferably, the preparation method comprises the steps of:
1) Mixing water and cyclohexane to prepare an aqueous cyclohexane solution;
2) Adding a cyclohexane solution containing the procatalyst to the aqueous cyclohexane solution;
3) Adding a cyclohexane solution containing the alkyl aluminum compound to the solution obtained in the step 2) to obtain the catalyst composition.
7. The method according to claim 6, wherein the concentration of the main catalyst in the cyclohexane solution containing the main catalyst is 0.1 to 50. Mu. Mol/mL, preferably 1 to 10. Mu. Mol/mL; and/or the concentration of the alkyl aluminum compound in the cyclohexane solution containing the alkyl aluminum compound is 100 mu mol/mL-1500 mu mol/mL, preferably 500 mu mol/mL-1000 mu mol/mL.
8. The production method according to claim 6 or 7, wherein the volume ratio of the aqueous cyclohexane solution, the cyclohexane solution containing the main catalyst and the cyclohexane solution containing the alkylaluminum compound is (80-99): (0.5-10), preferably (80-98): (1-10), more preferably (90-98): (1-5).
9. Use of the catalyst composition according to any one of claims 1 to 5 or the catalyst composition prepared according to the preparation process of any one of claims 6 to 8 in the field of olefin oligomerization, in particular in the field of ethylene oligomerization.
10. The application according to claim 9, wherein the conditions of the application comprise: the temperature is 10 to 90 ℃, preferably 40 to 75 ℃, more preferably 50 to 70 ℃, still more preferably 55 to 70 ℃.
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