CN106925348B - catalyst and application thereof - Google Patents
catalyst and application thereof Download PDFInfo
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- CN106925348B CN106925348B CN201511021457.1A CN201511021457A CN106925348B CN 106925348 B CN106925348 B CN 106925348B CN 201511021457 A CN201511021457 A CN 201511021457A CN 106925348 B CN106925348 B CN 106925348B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005977 Ethylene Substances 0.000 claims abstract description 49
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 30
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 40
- -1 2,4,6- trimethylphenyl Chemical group 0.000 claims description 38
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical class ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 4
- OZKRURPNXOGYGD-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1 OZKRURPNXOGYGD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004821 1,3-dichlorobenzenes Chemical class 0.000 claims description 3
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical class CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 76
- 239000012442 inert solvent Substances 0.000 abstract 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 57
- 229910052739 hydrogen Inorganic materials 0.000 description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 238000010790 dilution Methods 0.000 description 16
- 239000012895 dilution Substances 0.000 description 16
- 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 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 14
- 239000005457 ice water Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910000071 diazene Inorganic materials 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- BUQMVYQMVLAYRU-UHFFFAOYSA-N 1,1,2,3-tetrachloropropane Chemical compound ClCC(Cl)C(Cl)Cl BUQMVYQMVLAYRU-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- DXJLFETWXVDMLH-UHFFFAOYSA-N CCC1=CC(=N)CC(=N)C1 Chemical compound CCC1=CC(=N)CC(=N)C1 DXJLFETWXVDMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- INGGGNUCWJHFKD-UHFFFAOYSA-N chromium;pyridine Chemical compound [Cr].C1=CC=NC=C1 INGGGNUCWJHFKD-UHFFFAOYSA-N 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—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
- B01J31/143—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 of aluminium
-
- 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
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
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- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst and application thereof, wherein the catalyst consists of a chromium compound a, a N-containing compound b, an electron donor c and a cocatalyst d, and the molar ratio of the four components is 1: 2-10: 8-100: 40-2000; the catalyst is used for catalyzing ethylene oligomerization to synthesize decene, the oligomerization is carried out in an inert solvent, in an ethylene oligomerization high-pressure reaction kettle, the catalyst is prepared in situ in the inert solvent according to effective amount of a certain proportion of each component of the catalyst, ethylene is continuously introduced immediately, the catalyst is fully contacted with the ethylene, the oligomerization reaction is carried out, and the selectivity of the catalyst decene is more than 50 percent.
Description
Technical field
The present invention relates to a kind of catalyst and its applications, and in particular to the catalyst for ethylene oligomerization synthesis decene.
Background technique
As a kind of olefin product with high added value, the synthesis of decene is with application always by the attention of height.Mesh
Preceding domestic production decene can only rely on wax destructive distillation method, and this method C10 yield is low, accounts for 20% of product or so, impurity content
Height, and starving；Foreign countries use ethylene oligomerization technology, are able to produce decene, but selectivity time is low, highest accounts for product
20% or so.The present invention, can be by decene selectively improve to 50% by changing catalyst ligand and process conditions, and produces
There is no oligomer in object.
A kind of ethylene oligomerisation catalyst composition, including the positive propiono -1,10- of chlorination 2- are disclosed in CN 104107723
Phenanthroline contract amine iron, containing aluminum cocatalyst, which is used for ethylene oligomerization, there is very high oligomerisation reaction activity,
Technology prejudice of the field technical staff about water is overcome, even if still there is extraordinary activity in low aluminium/iron ratio,
Alpha-olefin selectivity is high, but C6~C10 alkene accounts for 51% altogether.
A kind of chromium system catalyst system is reported in EP 0608447A, as the catalyst of ethylene oligomerization, wherein including one kind
Containing chromium compound, azole compounds, containing aluminum cocatalyst, halogen contained compound as promotor, which selects hexene -1
Selecting property is higher, and can generate 3% decene.
In the ethylene oligomerization technique of W02004/05647, changing ligand, octene content reaches 69%, and ahexene content is 10~
20%, decene content is 4%.
There is no a kind of ethylene oligomerisation catalysts, and ethylene selectivity oligomerisation can be made to synthesize decene at present, and the present invention presses right
It is required that the catalyst described in 1 for ethylene oligomerization synthesis decene, can be catalyzed ethylene oligomerization high selectivity decene, decene
Selectivity is greater than 50%.
Summary of the invention
It include a kind of chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d the purpose of the present invention is developing a kind of
Composition, the catalyst synthesize decene for ethylene oligomerization, make chromium compounds under the action of ligand and promotor, form unoccupied orbital,
Be conducive to the coordination of ethylene molecule or alpha-olefin molecule, and β-H elimination reaction occurs and generates decene.During the test not
It was found that there is the oligomer of by-product to generate.
The present invention provides a kind of catalyst, including following component:
Chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d；
A, the molar ratio of b, c and d be 1:2~10:8~100:40~2000, more preferably 1:2~6:8~20:50~
200。
Catalyst of the present invention, wherein the chromium compounds a is preferably isooctyl acid chromium, chromium acetylacetonate and 2- formic acid
One or more of pyridine chromium.
Catalyst of the present invention, wherein the b of compound containing N, general formula are preferably
Catalyst of the present invention, wherein R1Preferably methyl, ethyl, isopropyl or tert-butyl；
R2Preferably phenyl, o-tolyl, tolyl, p-methylphenyl, 2,4,6- trimethylphenyl, adjacent ethylbenzene,
It is ethylbenzene, different to ethylbenzene, 4- tert-butyl-phenyl, 2- isopropyl phenyl, 3- isopropyl phenyl, 4- isopropyl phenyl, 2,6- bis-
Fluoro- 4 aminomethyl phenyl of propyl phenyl, naphthalene, fluorophenyl, 2-, the fluoro- 5- aminomethyl phenyl of 2-, 3- chlorphenyl, 2,6- dichlorophenyl, 2,
The bromo- 4- aminomethyl phenyl of 4,6- trichlorophenyl, 2- bromophenyl, 2-, the bromo- 5- aminomethyl phenyl of 2-, the bromo- 2,6- 3,5-dimethylphenyl of 4-, 4-
Methoxyphenyl or 2- methyl -4- methoxyphenyl.
Catalyst of the present invention, wherein the electron donor c is preferably 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1, and 1,
One or more of tetra- chloropropane of 2- trichloroethanes, tert-butyl chloride and 1,1,2,3-.
Catalyst of the present invention, wherein the co-catalyst d is preferably trimethyl aluminium, triethyl aluminum, three normal-butyls
One or more of aluminium, triisobutyl aluminium and aluminium diethyl monochloride.
The present invention also provides application of the above-mentioned catalyst in ethylene oligomerization synthesis decene.
A and b are added into flask, add quantitative inertia calibration object, c and d are added in syringe, by syringe
Being put into microwave radiometer has certain time taking-up, is added into the flask equipped with a and b, and flask vacuumizes at 40 DEG C, then to
The dilution of 20mL solvent is added in it, and dilution is directly added into the reaction kettle of hydrogen shield, is passed through ethylene and starts oligomerisation reaction.Reaction temperature
Degree is usually 40 DEG C~120 DEG C, preferably 65 DEG C~110 DEG C；Reaction pressure be 0.2MPa~4MPa, preferably 1MPa~
4MPa；Reaction time is 0.1h~4h, preferably 0.3~1.5h.
Ethylene oligomerization reaction mainly carries out in atent solvent.Selectable solvent includes alkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene
Hydrocarbon or ionic liquid；Alkane is n-hexane, hexahydrotoluene, hexamethylene or heptane；Aromatic hydrocarbons is benzene,toluene,xylene or isopropyl
Benzene；Alkene is hexene -1 or octene-1.
Beneficial effects of the present invention:
There is no oligomer generation in active high, decene selectivity height and by-product.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Embodiment 1
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds 2- formic acid
Pyridine chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentane 0.06mmol；1,1,2,3- tetrachloro is taken with syringe
Propane 0.24mmol and triethyl aluminum 0.15mL (1.2mmol), makes the molar ratio 1:2:8:40 of a, b, c and d.Syringe is put
Enter in microwave radiometer and be added in reaction flask after 10min, vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization reacts
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL toluene solvant is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, catalyst is added under hydrogen shield
In kettle, it is then quickly passed through ethylene, pressure 3MPa is kept, reacts 1h at 60 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 2
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds 2- formic acid
Pyridine chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentane 0.3mmol；1,1,2,3- tetrachloro is taken with syringe
Propane 0.48mmol and aluminium diethyl monochloride 0.4mL (3mmol), makes the molar ratio 1:10:8:100 of a, b, c and d.It will injection
Device is put into microwave radiometer after 10min and is added in reaction flask, vacuumizes at 40 DEG C, and it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL toluene solvant is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, catalyst is added under hydrogen shield
In kettle, it is then quickly passed through ethylene, pressure 3MPa is kept, reacts 1h at 60 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 3
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds 2- formic acid
Pyridine chromium 0.03mmol, N, N- di-o-tolyl -2,4- di-imidogen pentane 0.12mmol；1,1,2,3- tetrachloro is taken with syringe
Propane 3mmol and aluminium diethyl monochloride 7.5mL (60mmol), makes the molar ratio 1:8:100:2000 of a, b, c and d.It will injection
Device is put into microwave radiometer after 10min and is added in reaction flask, vacuumizes at 40 DEG C, and it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL toluene solvant is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, catalyst is added under hydrogen shield
In kettle, it is then quickly passed through ethylene, pressure 3MPa is kept, reacts 1h at 60 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 4
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.03mmol, N, N- bis- is to ethylbenzene -3,5- diimine in heptan 0.06mmol；With syringe take 1,2- dichloro-benzenes 0.24mmol and
Trimethyl aluminium 0.36mL (3mmol) makes the molar ratio 1:2:8:100 of a, b, c and d.Syringe is put into microwave radiometer
It is added in reaction flask after 10min, is vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL n-hexane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 3.5MPa, react 1h at 80 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 5
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds levulinic
Ketone chromium 0.03mmol, N, N- be bis--(4- tert-butyl-phenyl) -3,5- diimine in heptan 0.06mmol；1,3- dichloro-benzenes is taken with syringe
0.3mmol and triethyl aluminum 0.72mL (6mmol), makes the molar ratio 1:2:10:200 of a, b, c and d.Syringe is put into micro-
It is added in reaction flask after 10min in wave emitter, is vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL cyclohexane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 4MPa, react 0.5h at 100 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 6
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.015mmol, chromium acetylacetonate 0.015mmol, N, N- be bis--(4- tert-butyl-phenyl) -3,5- diimine in heptan 0.3mmol；With
Syringe takes 1,1,2- trichloroethanes 0.24mmol and aluminium diethyl monochloride 0.72mL (6mmol), makes the molar ratio of a, b, c and d
For 1:10:8:200.Syringe is put into microwave radiometer after 10min and is added in reaction flask, vacuumizes, adds at 40 DEG C
The dilution of 20mL hexamethylene is spare.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL cyclohexane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 4MPa, react 0.5h at 100 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 7
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.03mmol, N, N- be bis--(4- tert-butyl-phenyl) -2,6- dimethyl -3,5- diimine in heptan 0.3mmol；1 is taken with syringe,
1,2- trichloroethanes 1.5mmol and triisobutyl aluminium 0.6mL (3mmol), makes the molar ratio 1:10:50:100 of a, b, c and d.
Syringe is put into microwave radiometer after 10min and is added in reaction flask, is vacuumized at 40 DEG C, the dilution of 20mL hexamethylene is added
It is spare.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL methyl cyclohexane alkane solvents are added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, it will catalysis under hydrogen shield
Agent is added in kettle, is then quickly passed through ethylene, keeps pressure 2.5MPa, reacts 1h at 110 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 8
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds levulinic
Ketone chromium 0.03mmol, N, N- be bis--penta diimine 0.12mmol of (2- isopropyl phenyl) -2,4-；1,2- dichloro-benzenes is taken with syringe
1.5mmol, 1,1,2,3- tetra- chloropropane 1.5mmol and aluminium diethyl monochloride 7.2mL (60mmol), make the molar ratio of a, b, c and d
For 1:4:100:2000.Syringe is put into microwave radiometer after 10min and is added in reaction flask, is vacuumized at 40 DEG C, then plus
It is spare to enter the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
- 1 solvent of 200mL hexene is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 2MPa, react 2h at 100 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 9
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.015mmol, 2- pyridine carboxylic acid chromium 0.015mmol, N, N- be bis--(2,6- diisopropyl phenyl) -2,6- dimethyl -3,5- heptan
Diimine 0.3mmol；Take 1,1,2,2- tetrachloroethanes 1.5mmol and three n-butylaluminum 3.6mL (30mmol) with syringe, make a,
B, the molar ratio of c and d is 1:10:50:1000.Syringe is put into microwave radiometer after 10min and is added in reaction flask, 40 DEG C
Under vacuumize, add 20mL hexamethylene dilution it is spare.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL octene-1 solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 1.5MPa, react 2h at 110 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 10
1. the preparation of catalyst
2mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from through N2 as internal standard, adds isooctyl acid
Chromium 0.03mmol, N, N- dinaphthyl -2,2,6,6- tetramethyl -3,5- diimine in heptan 0.3mmol；1,1,2,3- tetra- is taken with syringe
Chloropropane 1.5mmol, trimethyl aluminium 0.54mL (7.5mmol), triethyl aluminum 0.9mL (7.5mmol), make mole of a, b, c and d
Than for 1:4:20:500.Syringe is put into microwave radiometer after 10min and is added in reaction flask, is vacuumized at 40 DEG C, then plus
It is spare to enter the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL heptane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, catalyst is added under hydrogen shield
In kettle, it is then quickly passed through ethylene, pressure 3MPa is kept, reacts 3h at 50 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 11
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.03mmol, N, N- be bis--(4- tert-butyl-phenyl) -2,6- dimethyl -3,5- diimine in heptan 0.15mmol；Chlorine is taken with syringe
For tertiary butane 1.2mmol, 1,1,2- trichloroethanes 1.2mmol and triisobutyl aluminium 0.36mL (3mmol) make rubbing for a, b, c and d
You are than being 1:6:40:100.Syringe is put into microwave radiometer after 10min and is added in reaction flask, is vacuumized at 40 DEG C, then
It is spare that the dilution of 20mL hexamethylene is added.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL methyl cyclohexane alkane solvents are added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, it will catalysis under hydrogen shield
Agent is added in kettle, is then quickly passed through ethylene, keeps pressure 2.5MPa, reacts 1h at 110 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 12
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds levulinic
Ketone chromium 0.015mmol, 2- pyridine carboxylic acid chromium 0.015mmol, N, N- dinaphthyl -2,2,6,6- tetramethyl -3,5- diimines in heptan
0.3mmol；With syringe take tetra- chloropropane 1mmol of 1,2- dichloro-benzenes 1mmol, 1,1,2- trichloroethanes 1mmol, 1,1,2,3- and
Three n-butylaluminum 3mL (15mmol), make the molar ratio 1:10:100:500 of a, b, c and d.Syringe is put into microwave radiometer
It is added in reaction flask after middle 10min, is vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL heptane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, catalyst is added under hydrogen shield
In kettle, it is then quickly passed through ethylene, pressure 3MPa is kept, reacts 3h at 50 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 13
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds levulinic
Ketone chromium 0.01mmol, 2- pyridine carboxylic acid chromium 0.02mmol, N, N- be bis--penta diimine 0.12mmol of (2- isopropyl phenyl) -2,4-；
Tert-butyl chloride 3mmol, triethyl aluminum 0.9mL (7.5mmol) and aluminium diethyl monochloride 0.54mL are taken with syringe
(4.5mmol) makes the molar ratio 1:4:10:400 of a, b, c and d.Syringe is put into microwave radiometer after 10min and is added
It in reaction flask, is vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
- 1 solvent of 200mL hexene is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 2MPa, react 2h at 100 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Embodiment 14
1. the preparation of catalyst
Through N22mL ethylbenzene is added in the 100mL reaction flask with stirring being sufficiently displaced from as internal standard, adds isooctyl acid
Chromium 0.015mmol, chromium acetylacetonate 0.015mmol, N, N- be bis--(4- tert-butyl-phenyl) -3,5- diimine in heptan 0.3mmol；With
Syringe takes tetra- chloropropane 0.24mmol of 1,1,2- trichloroethanes 0.24mmol, 1,1,2,3-, triethyl aluminum 0.9mL
(7.5mmol) and aluminium diethyl monochloride 0.72mL (6mmol), makes the molar ratio 1:10:16:700 of a, b, c and d.By syringe
It is put into microwave radiometer after 10min and is added in reaction flask, vacuumized at 40 DEG C, it is spare to add the dilution of 20mL hexamethylene.
2. ethylene oligomerization
The autoclave of 500mL vacuumizes 1h under heating state, is replaced 3 times using hydrogen, and under hydrogen protection
200mL cyclohexane solvent is added, pours hydrogen shield in kettle, 40 DEG C will be risen in reaction kettle, add catalyst under hydrogen shield
Enter in kettle, be then quickly passed through ethylene, keeps pressure 4MPa, react 0.5h at 100 DEG C.
Cooled down after reaction with ice water, release terminates reaction with the acidic ethanol of mass fraction 10%.As a result 1 is seen attached list.
Subordinate list 1
It can be seen from Table 1 that: the catalyst chromium compound a, the b of compound containing N, electron donor c, co-catalyst d, four groups
Divide under certain proportion, ethylene oligomerization can be catalyzed, decene selectivity reachable 63% in product, active up to 11.8 ×
106g/molCr.h。
Claims (2)
1. a kind of catalyst, including following component:
Chromium compounds a, the b of compound containing N, electron donor c, co-catalyst d；
A, the molar ratio of b, c and d are 1:2~10:8~100:40~2000；
Wherein, the b of compound containing N, general formula are as follows:
Wherein, the R1For methyl, ethyl, isopropyl or tert-butyl；
The R2For phenyl, o-tolyl, tolyl, p-methylphenyl, 2,4,6- trimethylphenyl, adjacent ethylbenzene, ethylbenzene
Base, to ethylbenzene, 4- tert-butyl-phenyl, 2- isopropyl phenyl, 3- isopropyl phenyl, 4- isopropyl phenyl, 2,6- diisopropyl
Fluoro- 4 aminomethyl phenyl of phenyl, naphthalene, fluorophenyl, 2-, the fluoro- 5- aminomethyl phenyl of 2-, 3- chlorphenyl, 2,6- dichlorophenyl, 2,4,6-
The bromo- 4- aminomethyl phenyl of trichlorophenyl, 2- bromophenyl, 2-, the bromo- 5- aminomethyl phenyl of 2-, the bromo- 2,6- 3,5-dimethylphenyl of 4-, 4- methoxy
Base phenyl or 2- methyl -4- methoxyphenyl；
The chromium compounds a is one or more of isooctyl acid chromium, chromium acetylacetonate and 2- pyridine carboxylic acid chromium；
The electron donor c is 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,1,2- trichloroethanes, tert-butyl chloride and 1,1,2,3-
One or more of four chloropropanes；
The co-catalyst d is in trimethyl aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium and aluminium diethyl monochloride
It is one or more of.
2. application of the catalyst described in claim 1 in ethylene oligomerization synthesis decene.
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