CN101720253A - 用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法 - Google Patents
用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法 Download PDFInfo
- Publication number
- CN101720253A CN101720253A CN200880022945A CN200880022945A CN101720253A CN 101720253 A CN101720253 A CN 101720253A CN 200880022945 A CN200880022945 A CN 200880022945A CN 200880022945 A CN200880022945 A CN 200880022945A CN 101720253 A CN101720253 A CN 101720253A
- Authority
- CN
- China
- Prior art keywords
- carbon monoxide
- olefin polymeric
- chromium
- preferred
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 239000005977 Ethylene Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 20
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 10
- JCALBVZBIRXHMQ-UHFFFAOYSA-N [[hydroxy-(phosphonoamino)phosphoryl]amino]phosphonic acid Chemical group OP(O)(=O)NP(O)(=O)NP(O)(O)=O JCALBVZBIRXHMQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000011651 chromium Substances 0.000 claims description 25
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- -1 cyclic aliphatic hydrocarbon Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 2
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical compound [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 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
- 125000005023 xylyl group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000002524 organometallic group Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- OPQBRAZQWOSDBN-UHFFFAOYSA-N chromium phosphane Chemical compound P.P.[Cr] OPQBRAZQWOSDBN-UHFFFAOYSA-N 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- CQWZFXYGTYPDHT-UHFFFAOYSA-N C(C)(C)NPC1=CC=CC=C1 Chemical class C(C)(C)NPC1=CC=CC=C1 CQWZFXYGTYPDHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- YFYIWIZSIVZILB-UHFFFAOYSA-N N.[P] Chemical compound N.[P] YFYIWIZSIVZILB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- UZEDIBTVIIJELN-UHFFFAOYSA-N chromium(2+) Chemical compound [Cr+2] UZEDIBTVIIJELN-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 235000015073 liquid stocks Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
-
- 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
- B01J31/1845—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 phosphorus
- B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
-
- 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
- B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one 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
-
- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6587—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
-
- 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
- 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
- C07C2531/24—Phosphines
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法。其中所述催化剂组合物包含一种铬化合物;一种结构通式为(A)R1R2P-N(R3)-P(R4)-N(R5)-H或(B)R1R2P-N(R3)-P(R4)-N(R5)-PR6R7或(A)和(B)的任意环状衍生物的配体,其中PNPN单元或PNPNP单元的P或N原子中的至少一个是环状体系的元素,所述环状体系由一个或多个结构(A)或(B)的构成化合物通过取代形成;和一种活化剂或助催化剂。
Description
本发明涉及用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法。
制备线性α-烯烃(LAO)、包括共聚单体级1-己烯和1-辛烯的现有方法依赖乙烯的低聚。这些方法的共同点是它们都会产生链长为4、6、8等的乙烯低聚物的产品分布。这归因于其化学机理很大程度上由竞争性链增长和链转移反应步骤控制,从而导致舒尔茨-弗洛里(Schulz-Flory)或泊松(Poisson)产品分布。
从市场角度来看,这种产品分布给所有的α-烯烃生产商都提出了难以应对的挑战。原因在于,根据市场的规模和发展、地理位置、细化程度等,每个供应的市场段都表现出极其不同的状况。因此生产商很难适应市场需求,因为部分产品在特定经济环境下的需求很高,而与此同时其他产品馏分可能根本没有市场或仅存在边缘需要。目前,聚合物产业中价值最高的LAO产品是共聚单体级1-己烯,而对1-辛烯的需求也在迅速增长。
因此,针对性地制备最经济可行的LAO、即共聚单体级1-己烯和1-辛烯显得非常合乎需求。为满足对高C6选择性和/或C8选择性的需求,已开发了新的方法。仅知的选择性C6的工业方法由Chevron Phillips投入使用,参见例如J.T.Dixon、M.J.Green、F.M.Hess、D.H.Morgan,“Advances inselective ethylene trimerisation-a critical overview”,Journal ofOrganometallic Chemistry,689(2004):3641-3668等综述。
此外,萨索尔(Sasol)已提交了专利申请(WO 93/053891A1),公开了基于铬的选择性乙烯三聚催化剂体系,代表类型为CrCl3(双(2-二苯基膦-乙基)胺)/MAO(甲基铝氧烷)。而且还公开了配体结构的变体(例如双(2-二乙基膦-乙基)胺、五甲基二乙烯三胺等)。然而,所有这些络合物都产生大量不想要的副产物,如除1-己烯外的LAO和聚乙烯。
大量科学出版物和专利文献记载了基于铬的金属有机络合物在乙烯的三聚和四聚中的应用,所述络合物带有特征为基本PNP结构的配体(例如双(二苯基膦基)胺配体)(D.S.McGuinness,P.Wasserscheid,W.Keim,C.Hu,U.Englert,J.T.Dixon,C.Grove,“Novel Cr-PNP complexes ascatalysts for the trimerization of ethylene”,Chem.Commun.,2003,334-335;K.Blann,A.Bollmann,J.T.Dixon,F.M.Hess,E.Killian,H.Maumela,D.H.Morgan,A.Neveling,S.Otto,M.J.Overett,“Highlyselective chromium-based ethylene trimerisation catalysts with bulkydiphosphinoamine ligands”,Chem.Comm.,2005,620-621;M.J.Overett,K.Blann,A.Bollmann,J.T.Dixon,F.Hess,E.Killian,H.Maumela,D.H.Morgan,A.Neveling,S.Otto,“Ethylene trimerisation and tetramerisationcatalysts with polar-substituted diphosphinoamine ligands”,Chem.Commun.,2005,622-624;A.Jabri,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau,“Isolation of a Cationic Chromium(II)Species ina Catalytic System for Ethylene Tri-and Tetramerization”,Organometallics,2006,25,715-718;T.Agapie,S.J.Schofer,J.A.Labinger,J.E.Bercaw,“Mechanistic Studies of the Ethylene TrimerizationReaction with Chromium-Diphosphine Catalysts:Experimental Evidencefor a Mechanism Involving Metallacyclic Intermediates”,J.Am.Chem.Soc.,2004,126,1304-1305;S.J.Schofer,M.D.Day,L.M.Henling,J.A.Labinger,J.E.Bercaw,“Ethylene Trimerization Catalysts Based onChromium Complexes with a Nitrogen-Bridged Diphosphine LigandHaving ortho-Methoxyaryl or ortho-Thiomethoxy Substituents:Well-Defined Catalyst Precursors and Investigations of the Mechanism”,Organometallics,2006,25,2743-2749;S.J.Schofer,M.D.Day,L.M.Henling,J.A.Labinger,J.E.Bercaw,“A Chromium-Diphosphine Systemfor Catalytic Ethylene Trimerization:Synthetic and Structural Studies ofChromium Complexes with a Nitrogen-Bridged Diphosphine Ligand withortho-Methoxyaryl Substituents”,Organometallics,2006,25,2733-2742;P.R.Elowe,C.McCann,P.G.Pringle,S.K.Spitzmesser,J.E.Bercaw,“Nitrogen-Linked Diphosphine Ligands with Ethers Attached to Nitrogenfor Chromium-Catalyzed Ethylene Tri-and Tetramerization”,Organometallics,2006,25,5255-5260;WO 2004/056578,WO 2004/056479,EP 02794480.0,EP 02794479.2)或带有特征为SNS结构的配体(D.S.McGuinness,D.B.Brown,R.P.Tooze,F.M.Hess,J.T.Dixon,A.M.Z.Slavin,“Ethylene Trimerization with Cr-PNP and Cr-SNS Complexes:Effect of Ligand Structure,Metal Oxidation State,and Role of Activatoron Catalysis”,Organometallics,2006,25,3605-3610;A.Jabri,C.Temple,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau,“Role of theMetal Oxidation State in the SNS-Cr Catalyst for Ethylene Trimerization:Isolation of Di-and Trivalent Cationic Intermediates”,J.Am.Chem.Soc.,2006,128,9238-9247;C.Temple,A.Jabri,P.Crewdson,S.Gambarotta,I.Korobkov,R.Duchateau,“The Question of the Cr-Oxidation State in the{Cr(SNS)}Catalyst for Selective Ethylene Trimerization:AnUnanticipated Re-Oxidation Pathway”,Angew.Chem.Int.Ed.,2006,45,7050-7053)。过量的MAO常用作活化剂/助催化剂。
尽管大部分已公开的研究依赖于Cr-PNP络合物,但也有一些使用其他配体,例如通式(R1)(R2)P-X-P(R3)(R4)的配体(其中X为二价有机桥连基,见WO 2005/039758A1),或使用完全不同的络合物,如二茂钛(H.Hagen,W.P.Kretschmer,F.R.van Buren,B.Hessen,D.A.van Oeffelen,“Selective ethylene trimerization:A study into the mechanism and thereduction of PE formation”,Journal of Molecular Catalysis A:Chemical,248(2006):237-247)。无论哪种情况,关注的重点总为选择性以及使聚乙烯的形成最小化。
迄今为止在科学和专利文献中公开的乙烯三聚和四聚催化剂和方法通常具有一种或多种下列缺陷:
●所需产物1-己烯和/或1-辛烯的选择性低(由副反应渠道产生的不需要的副产物)。
●产物纯度有限,例如在特定C6或C8馏分内的选择性有限(异构化、支链烯烃形成等)。
●形成蜡,即形成重的长链高碳数产物。
●形成聚合物(聚乙烯、支化和/或交联的PE);这导致显著的产量损失和设备附着。
●转换率/催化剂活性差,这导致每千克产物成本高。
●催化剂或配体成本高。
●配体合成困难,这导致实用性差和催化剂成本高。
●催化剂的活性和选择性对微量杂质敏感(催化剂损失/中毒)。
●催化剂成分在技术环境中处理困难(催化剂络合物的合成、预混、钝化,催化剂或配体的回收)。
●反应条件苛刻,即高温和高压,这导致投入、维护和能源成本高。
●助催化剂/活化剂的成本和/或消耗高。
●对助催化剂质量的变化敏感;当必须使用大量质量较差的化合物作活化剂时常常如此(例如某些MAO类)。
本发明的一个目标是提供克服现有技术缺陷的用于乙烯的选择性二聚、三聚和/或四聚的催化剂组合物和方法。尤其是,无论工艺条件如何,都可取得较高的选择性而且避免形成大量的蜡和聚合物。另外,所述催化剂组合物也应为技术方法提供足够高的活性转换率。
换言之,应避免现有技术中广谱的LAO(线性α-烯烃)产物,而能够选择性制备优选的经济上最需要的产物1-己烯。根据助催化剂的性质和反应条件,还应能分别提供共同产物例如1-丁烯和1-己烯,以及1-己烯和1-辛烯。
所述目标通过一种催化剂组合物实现,其包括:
(a)一种铬化合物;
(b)一种配体,其结构通式为
(A)R1R2P-N(R3)-P(R4)-N(R5)-H,或
(B)R1R2P-N(R3)-P(R4)-N(R5)-PR6R7,
其中R1、R2、R3、R4、R5、R6和R7独立地选自卤素、氨基、三甲基甲硅烷基、C1-C10烷基、芳基和取代芳基;或者
(A)和(B)的任意环状衍生物,其中PNPNP单元或PNPN单元的P或N原子中的至少一个是环体系中的元素,所述环体系由一个或多个结构(A)或(B)的构成化合物通过取代形成;
(c)一种活化剂或助催化剂。
应当理解,(A)和(B)的任意环状衍生物均可用作配体,其中PNPN单元(结构(A))或PNPNP单元(结构(B))的P或N原子中的至少一个是环元素,所述环由一个或多个结构(A)或(B)的构成化合物通过取代形成,即形式上消去每个构成化合物的两个完整基团R1-R7(如定义的)或H、两个基团R1-R7(如定义的)中各自的一个原子、或者一个完整基团R1-R7(如定义的)或H和另一个基团R1-R7(如定义的)中的一个原子,并且形式上由此产生的每个构成化合物中的不饱和价态位置通过一个共价键连接,以使其价态与给定位置的原始价态相同。
适宜的(A)和(B)的环状衍生物可为如下结构:
优选地,所述铬化合物选自Cr(II)或Cr(III)的有机盐或无机盐、配位络合物和有机金属络合物。
最优选地,所述铬化合物选自CrCl3(THF)3、乙酰丙酮铬(III)、辛酸铬(III)、六羰基铬、2-乙基己酸铬(III)和(苯)三羰基铬。
R1、R2、R3、R4、R5、R6和R7还优选选自氯、氨基、三甲基甲硅烷基、甲基、乙基、异丙基、叔丁基、苯基、苯甲基、甲苯基和二甲苯基。
适宜的具有氨基取代基的配体(A)和(B)可为如下结构:
在一个实施方案中,所述活化剂或助催化剂选自三甲基铝、三乙基铝、三异丙基铝、三异丁基铝、三乙基三氯化二铝、二乙基氯化铝、乙基二氯化铝、甲基铝氧烷(MAO)、或其混合物。
最优选地,所述配体选自(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(t-Bu)-H和(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H。
还优选提供一种包含溶剂的催化剂组合物。
优选地,所述溶剂选自芳香烃类、直链和环状的脂肪烃类、直链烯烃以及醚,优选甲苯、苯、乙苯、异丙苯、二甲苯、均三甲苯、己烷、辛烷、环己烷、甲基环己烷、己烯、庚烯、辛烯、二乙基醚或四氢呋喃,最优选甲苯。也可使用这些溶剂的任意混合物。
在一个实施方案中,铬化合物的浓度为0.01至100mmol/l,优选0.1至10mmol/l。
配体/Cr的比例优选为0.5至50,优选0.8至2.0。
Al/Cr的比例优选为1至1000,优选10至200。
对本领域的技术人员显而易见的是,用于提供催化剂组合物的组分(a)至(c)可或多或少地当作起始原料,而当混合三种化合物(a)-(c)时可发生转化以形成催化剂组合物。在这点上,本发明的催化剂组合物也可阐述为可通过使至少下列物质结合而获得:
(a)一种铬化合物;
(b)一种配体,其结构通式为
(A)R1R2P-N(R3)-P(R4)-N(R5)-H,或
(B)R1R2P-N(R3)-P(R4)-N(R5)-PR6R7,
其中R1、R2、R3、R4、R5、R6和R7独立地选自卤素、氨基、三甲基甲硅烷基、C1-C10烷基、芳基和取代芳基;或者
(A)和(B)的任意环状衍生物,其中PNPN单元或PNPNP单元的P或N原子中的至少一个是环体系的元素,所述环体系由一个或多个结构(A)或(B)的构成化合物通过取代形成;以及
(c)一种活化剂或助催化剂。
本发明还提供一种乙烯二聚、三聚和/或四聚的方法,包括将本发明的催化剂组合物作用于反应器中的气相乙烯并进行低聚。
优选地,所述低聚在1至200bar、优选10至50bar的压力下进行。
同样优选地,所述低聚在10至200℃、优选20至100℃的温度下进行。
在一个实施方案中,所述方法连续、半连续或间断地进行。
平均停留时间可为10分钟至20小时,优选1至4小时。
当将结构通式(A)的配体和一种助催化剂结合时,可获得具有下列结构式的反应产物:
当然,以上公开的反应产物也可用于催化剂组合物中,以代替单独加入配体和助催化剂,这也应在本发明的保护范围之内。
在反应条件下,PNPN-H型的配体通过助催化剂原位去质子化。在本发明的另一个有利的实施方案中,活性催化剂也可通过单独的去质子/消去步骤以产生上面给出结构而非原位(ex-situ)形成。
尤其是,如果使用较小的或空间需求小的R1-R7基团,则配体趋向形成二聚体。这些二聚的环状偶磷氮烷可直接用来形成活性催化剂。
公开的配体结构通式(A)和(B)也可用以下结构式表示:
最优选的配体结构为(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H和
出乎意料地,发现使用本发明的用于乙烯二聚、三聚和四聚的催化剂组合物和方法可显著克服现有技术中的缺陷。尤其是,本发明的方法和催化剂组合物使得能够以高的转换率和选择性制备1-己烯。另外,还可获得较高的重现性,即所述催化剂组合物适于抵抗杂质和工艺条件波动的干扰。昂贵的助催化剂如MAO,可完全或较大程度地用较便宜物质、优选三乙基铝代替。另外,由于其较差界定的化学结构而倾向于质量不稳定的助催化剂(例如MAO)可部分或全部地用良好界定的化学物种(三乙基铝)代替。采用本发明的方法,不会得到宽的LAO产物分布,而可以选择性地制备特定的α-烯烃。另外,聚合物的形成也能够得到良好抑制。此外,还可选择温和的反应条件,从而实现工业规模装置上的低投资成本、以及低的能源成本和操作成本。另外,还可设计一种相对简单直接的方法。极高的1-己烯或1-己烯/1-辛烯选择性使得能够产生高的产品纯度,而无需在单独的生产线中进行额外的纯化步骤。
现将参照附图在以下实施例部分中对本发明的其它优点和特征进行说明,其中图1是实施例2中获得的液相的GC/FID分析。
活性催化剂可通过使铬源和配体在合适的溶剂(优选甲苯)中结合而制备,所述溶剂使得铬浓度为0.01至100mmol/l,优选0.1至10mmol/l,且配体/Cr的比例为03至50mol/mol,优选0.8至2.0mol/mol。助催化剂——优选三乙基铝、或三乙基铝和MAO或三乙基铝和三甲基铝的任意混合物——以甲苯溶液的形式加入,以使Al/Cr的比例为1至1000mol/mol。优选Al/Cr的比例为10至200mol/mol。
溶剂甲苯可用其他溶剂代替,如除甲苯外的芳香烃(苯、乙苯、异丙苯、二甲苯、均三甲苯等);脂肪烃(直链和环状,例如己烷、辛烷、环己烷);直链烯烃,如己烯、庚烯、辛烯等;或醚,如二乙基醚或四氢呋喃。
然后使催化剂溶液于1至200bar、优选10至50bar的压力下作用于在适宜的压力反应器中的气相干燥乙烯。所述反应器可以是适于使气相和液相充分接触的任何类型的反应器,如鼓泡塔反应器、搅拌釜反应器、具有固定或分布式乙烯注入的流动反应器等。
优选的反应温度为10至200℃,最优选的温度为20至100℃。对平均停留时间和停留时间分布(对于连续方法而言)进行选择,以便实现高选择性下的充分转化。平均停留时间通常为10分钟至20小时(取决于温度和压力)。优选的范围为1至4小时。
实施例1:配体的制备
1.1二(异丙基氨基)苯基膦(NPN)的制备
于0℃经过30分钟向搅拌的异丙基胺(30ml,352mmol)的***(250ml)溶液中加入二氯苯基膦(9.63ml,71mmol,溶于50ml二***中)。共搅拌72小时后过滤所述溶液。残留物用***洗涤,并真空除去溶剂。剩余的油状物在0.2托/76-78℃下蒸馏,得到无色液体,产率33%(5.3g)。31P{H}NMR:49.0ppm。
1.2(苯基)2PN(异丙基)P(苯基)NH(异丙基)(PNPN-H)的制备
将NPN类(如1.1节所制备)(2.4g,10.7mmol)的四氢呋喃(10ml)溶液于-40℃逐滴加入至搅拌的三乙胺(6ml)和氯二苯基膦(2.36g,10.7mmol)的四氢呋喃(40ml)溶液中。于室温下再搅拌24小时,之后滤出三乙基铵盐,并将残留物溶于正己烷中,再次过滤,所得溶液在-30℃下结晶。产率52%(2.3g,5.6mmol)。31P{H}NMR:41.2,68.4(宽峰)。
实施例2:乙烯三聚
将装有汲取管,温度计套管,气动搅拌器,冷却盘管,温度、压力和搅拌速度控制单元(均连接至数据采集***)的300ml压力反应器用干燥的氩气惰化,并填充100ml无水甲苯。将1694μl 4.017重量%的配体1((苯基)2PN(异丙基)P(苯基)NH(异丙基))的甲苯溶液与59.2mg CrCl3(thf)3(thf=四氢呋喃)在氩气氛围下混合。在持续氩气流下将催化剂溶液与3.6ml 1.9mol/l的三乙基铝的甲苯溶液转移至反应器中。
选用的体积和重量相当于在配体/CrCl3(thf)3的比例为1.5mol/mol且Al/Cr的比例为70mol/mol的条件下,铬浓度为1mmol/l。
将反应器密封,用干燥乙烯加压至30bar并加热至40℃。在1200rpm的搅拌下,通过数据采集***和对乙烯压力缸连续称重的电子天平来监测乙烯的消耗。在120分钟的停留时间之后,借助乙烯压力将液体存量转移至装有约100ml水的玻璃容器中以淬灭液相中的反应。反应器顶部空间的全部气相使用经校准的气量计定量测定,然后定量地收集在经吹扫并排空的气袋中。
在分离液体有机相之后,通过称重测定总质量。然后用GC/FID分析有机相的组成。之前收集的气相用GC/FID单独分析。
基于测量的数据,完成质量平衡(mass balance)并确定总产率和选择性。
为说明目的,图1中给出了液相的GC示图。出乎意料地,观察到极高的1-己烯产率,而仅有痕量的1-丁烯、1-辛烯、1-癸烯和1-十二烯。在归零的、良好界定的条件下重复实验,没有观察到可辨别的聚合物形成。40℃下C6的平均产率超过89重量%,并随温度升高略微降低。与高C6产率相比更出乎意料的是C6馏分内的1-己烯选择性。在40℃的反应温度下,测得的1-己烯选择性接近100重量%,即在实验误差内与100重量%没有区别,从而使得在工艺操作中无需使用任何精密分离单元来确保1-己烯规格。本发明公开的新型催化剂体系可非常有效地抑制任何不想要的副反应渠道,如烯烃异构或重排、溶剂的傅克烷基化(Friedel-Crafts-alkylation)、共同低聚等。
将一系列非最优化实验的代表性结果总结于表1中。尽管较高温度使C6产率降低,但是可用于共同制备C4烯烃和C6烯烃,同时还使C4和C6馏分内分别具有较高的1-丁烯和1-己烯选择性(产物纯度)。
表1:温度对C6产率和1-己烯选择性的影响(除温度外的工艺参数如实施例1中所规定)
使用不同的助催化剂和/或通过改变配体的官能团结构或Cr/配体比例,所述体系可由纯1-己烯(即乙烯三聚催化剂)转变为结合的三聚/四聚体系,从而高选择性地制备1-己烯和1-辛烯。
在使用配体1的情况下,三乙基铝作为助催化剂能够获得高的1-己烯产率,而MAO会产生1-己烯和1-辛烯。
助催化剂的结合,如带有少量MAO或三甲基铝的三乙基铝,可使总活性——即转化率——提高至少三倍,同时能够维持高的产率和选择性。
还如上所述成功地合成并测试了优选的PNPN-H结构的基本配体类型的其它变体。
在以上说明书、权利要求和附图中公开的特征,无论单独使用还是以其任意结合的形式使用,对于以各种形式实现本发明都是重要的。
Claims (17)
1.催化剂组合物,包含:
(a)一种铬化合物;
(b)一种配体,其结构通式为
(A)R1R2P-N(R3)-P(R4)-N(R5)-H,或
(B)R1R2P-N(R3)-P(R4)-N(R5)-PR6R7,
其中R1、R2、R3、R4、R5、R6和R7独立地选自卤素、氨基、三甲基甲硅烷基、C1-C10烷基、芳基和取代芳基;或者
(A)和(B)的任意环状衍生物,其中PNPN单元或PNPNP单元的P或N原子中的至少一个是环状体系的元素,所述环状体系由一个或多个结构(A)或(B)的构成化合物通过取代形成;和
(c)一种活化剂或助催化剂。
2.权利要求1的催化剂组合物,其中所述铬化合物选自Cr(II)或Cr(III)的有机盐或无机盐、配位络合物和有机金属络合物。
3.权利要求2的催化剂组合物,其中所述铬化合物选自CrCl3(THF)3、乙酰丙酮铬(III)、辛酸铬(III)、六羰基铬、2-乙基己酸铬(III)和(苯)三羰基铬。
4.上述权利要求中任一项的催化剂组合物,其中R1、R2、R3、R4、R5、R6和R7选自氯、氨基、三甲基甲硅烷基、甲基、乙基、异丙基、叔丁基、苯基、苯甲基、甲苯基和二甲苯基。
5.上述权利要求中任一项的催化剂组合物,其中所述活化剂或助催化剂选自三甲基铝、三乙基铝、三异丙基铝、三异丁基铝、三乙基三氯化二铝、二乙基氯化铝、乙基二氯化铝、甲基铝氧烷(MAO)、或其混合物。
6.上述权利要求中任一项的催化剂组合物,其中所述配体选自(Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(Ph)-H、(Ph)2P-N(i-Pr)-P(Ph)-N(t-Bu)-H和(Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H。
7.上述权利要求中任一项的催化剂组合物,还包含一种溶剂。
8.权利要求7的催化剂组合物,其中所述溶剂选自芳香烃、直链和环状脂肪烃、直链烯烃和醚,优选甲苯、苯、乙苯、异丙苯、二甲苯、均三甲苯、己烷、辛烷、环己烷、甲基环己烷、己烯、庚烯、辛烯、二乙基醚或四氢呋喃、或其混合物,最优选甲苯。
9.权利要求7或8的催化剂组合物,其中所述铬化合物的浓度为0.01至100mmol/l,优选0.1至10mmol/l。
10.上述权利要求中任一项的催化剂组合物,其中配体/Cr比例为0.5至50,优选0.8至2.0。
11.权利要求5的催化剂组合物,其中Al/Cr比例为1∶1至1000∶1,优选10∶1至200∶1。
12.催化剂组合物,通过使至少下列物质结合而获得:
(a)一种铬化合物;
(b)一种配体,其结构通式为
(A)R1R2P-N(R3)-P(R4)-N(R5)-H,或
(B)R1R2P-N(R3)-P(R4)-N(R5)-PR6R7,
其中R1、R2、R3、R4、R5、R6和R7独立地选自卤素、氨基、三甲基甲硅烷基、C1-C10烷基、芳基和取代芳基;或者
(A)和(B)的任意环状衍生物,其中PNPN单元或PNPNP单元的P或N原子中的至少一个是环状体系的元素,所述环状体系由一个或多个结构(A)或(B)的构成化合物通过取代形成;以及
(c)一种活化剂或助催化剂。
13.用于乙烯二聚、三聚和/或四聚的方法,包含使权利要求1至12中任一项的催化剂组合物作用于反应器中的气相乙烯并进行低聚。
14.权利要求13的方法,其中所述低聚在1至200bar、优选10至50bar的压力下进行。
15.权利要求13或14的方法,其中所述低聚在10至200℃、优选20至100℃的温度下进行。
16.权利要求13至15中任一项的方法,其中所述方法连续地进行。
17.权利要求13至16中任一项的方法,其中平均停留时间为10分钟至20小时,优选1至4小时。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07013543.9 | 2007-07-11 | ||
EP07013543 | 2007-07-11 | ||
PCT/EP2008/004815 WO2009006979A2 (en) | 2007-07-11 | 2008-06-16 | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101720253A true CN101720253A (zh) | 2010-06-02 |
CN101720253B CN101720253B (zh) | 2013-07-17 |
Family
ID=38863117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008800229456A Active CN101720253B (zh) | 2007-07-11 | 2008-06-16 | 用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法 |
Country Status (13)
Country | Link |
---|---|
US (2) | US8637721B2 (zh) |
EP (1) | EP2167231B8 (zh) |
JP (1) | JP5158726B2 (zh) |
KR (1) | KR101241656B1 (zh) |
CN (1) | CN101720253B (zh) |
BR (1) | BRPI0813779B1 (zh) |
CA (1) | CA2692533C (zh) |
ES (1) | ES2394866T3 (zh) |
MY (1) | MY148675A (zh) |
RU (1) | RU2456078C2 (zh) |
SG (1) | SG183005A1 (zh) |
TW (1) | TWI415683B (zh) |
WO (1) | WO2009006979A2 (zh) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102451759A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN102451758A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN103100420A (zh) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | 用于乙烯四聚的催化剂组合物及其中配体的制备方法 |
CN104511311A (zh) * | 2013-09-30 | 2015-04-15 | 华东理工大学 | 一种高选择性的乙烯三聚、四聚催化剂体系及其使用方法 |
CN106573236A (zh) * | 2014-07-24 | 2017-04-19 | 沙特基础工业全球技术有限公司 | 用于乙烯的低聚以产生1‑己烯和/或1‑辛烯的催化剂组合物和方法 |
CN109289928A (zh) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | 一种用于乙烯齐聚的催化剂及其制备方法 |
CN111434670A (zh) * | 2019-01-15 | 2020-07-21 | 中国石油化工股份有限公司 | 含氟化合物及用途和乙烯齐聚催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
CN111434668A (zh) * | 2019-01-15 | 2020-07-21 | 中国石油化工股份有限公司 | 含卤素化合物及用途和催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
WO2020147372A1 (zh) * | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | 含卤素化合物及其作为催化剂配体在乙烯齐聚中的用途 |
CN111889142A (zh) * | 2020-07-23 | 2020-11-06 | 天津科技大学 | 一种乙烯选择性齐聚的催化剂体系、反应方法及其应用 |
CN112473741A (zh) * | 2020-10-22 | 2021-03-12 | 杭州小菱科技有限公司 | 一种乙烯齐聚催化剂体系及其制备方法与用途 |
CN113260457A (zh) * | 2018-11-12 | 2021-08-13 | 沙特基础全球技术有限公司 | 用于铬辅助乙烯低聚工艺中生产1-己烯的配体 |
JP2022104240A (ja) * | 2020-12-28 | 2022-07-08 | 株式会社アビー | 細胞凍結保存液、及び細胞凍結方法 |
Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2010005266A (es) * | 2007-11-28 | 2010-06-02 | Linde Ag | Composicion catalizadora y proceso para oligomerizacion de etileno. |
ES2371218T3 (es) * | 2009-04-09 | 2011-12-28 | Saudi Basic Industries Corporation | Composición de catalizador y procedimiento para la oligomerización de etileno. |
CA2777323C (en) | 2009-10-16 | 2017-07-11 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream which includes ethylene |
WO2011085951A1 (en) | 2010-01-15 | 2011-07-21 | Basell Polyolefine Gmbh | Oligomerization of olefins |
EP2354113A1 (en) | 2010-02-04 | 2011-08-10 | Linde AG | Method for deactivation of a catalyst |
WO2012055943A2 (en) | 2010-10-28 | 2012-05-03 | Basell Polyolefine Gmbh | Oligomerization of olefins |
WO2012072178A1 (en) | 2010-11-30 | 2012-06-07 | Linde Aktiengesellschaft | Method for cleaning a reactor and/or equipment thereof |
EP2489431B1 (en) | 2011-02-16 | 2013-05-01 | Linde AG | Method for preparing a catalyst composition for oligomerization of ethylene and respective catalyst composition pre-formation unit |
JP5844636B2 (ja) * | 2011-12-27 | 2016-01-20 | 出光興産株式会社 | α−オレフィンの製造方法 |
KR101846031B1 (ko) | 2012-03-16 | 2018-04-05 | 에스케이이노베이션 주식회사 | 에틸렌으로부터 1-헥센 및/또는 1-옥텐을 제조하기 위한 촉매계 |
SG11201406965UA (en) | 2012-05-09 | 2014-11-27 | Sasol Tech Pty Ltd | Separation of components from a multi-component hydrocarbon stream |
CN104284714B (zh) | 2012-05-09 | 2016-06-29 | 沙索技术有限公司 | 用于使烃低聚以形成至少一种共聚单体产物的方法 |
ES2750659T3 (es) | 2012-05-09 | 2020-03-26 | Sasol Tech Pty Ltd | Tetramerización de etileno |
ES2656088T3 (es) | 2012-05-09 | 2018-02-23 | Sasol Technology (Proprietary) Limited | Tetramerización de etileno |
KR102088445B1 (ko) | 2012-05-09 | 2020-03-13 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | 중합체 형성이 감소된 올레핀 화합물의 올리고머화 |
EP2684857A1 (en) | 2012-07-10 | 2014-01-15 | Saudi Basic Industries Corporation | Method for oligomerization of ethylene |
KR101483248B1 (ko) | 2012-11-15 | 2015-01-16 | 주식회사 엘지화학 | 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매계, 이의 제조 방법 및 이를 이용한 에틸렌 올리고머화 방법 |
EP2738151B8 (en) * | 2012-11-28 | 2014-12-17 | Saudi Basic Industries Corporation | Process for oligomerization of ethylene |
CA2800268C (en) * | 2012-12-21 | 2020-02-25 | Nova Chemicals Corporation | Continuous ethylene tetramerization process |
EP2764915B1 (en) | 2013-02-11 | 2017-03-22 | Linde AG | Purification method for a crude PNPNH compound |
EP2764913A1 (en) | 2013-02-11 | 2014-08-13 | Linde AG | Method for purifying a crude PNPNH compound |
EP2764914A1 (en) | 2013-02-11 | 2014-08-13 | Linde AG | Metalated PNPNH ligand, catalyst composition and use thereof in the oligomerization of ethylene |
KR101483247B1 (ko) * | 2013-04-23 | 2015-01-16 | 주식회사 엘지화학 | 폴리올레핀 중합용 촉매의 제조 방법 및 폴리올레핀 제조방법 |
SG11201508463VA (en) | 2013-05-09 | 2015-11-27 | Sasol Tech Pty Ltd | Tetramerisation of ethylene |
KR20160006192A (ko) | 2013-05-09 | 2016-01-18 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | 에틸렌의 1-헥센 및 1-옥텐의 혼합물로의 올리고머화 방법 |
CA2908559C (en) | 2013-05-09 | 2021-08-17 | Sasol Technology (Proprietary) Limited | Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene |
EP2832445A1 (en) * | 2013-07-29 | 2015-02-04 | Linde AG | Catalyst composition and process for oligomerization of ethylene |
KR101638980B1 (ko) | 2013-09-30 | 2016-07-12 | 주식회사 엘지화학 | 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매 시스템, 및 이를 이용한 에틸렌 올리고머화 방법 |
KR101601936B1 (ko) | 2013-11-19 | 2016-03-09 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
EP3092074A2 (en) * | 2014-01-06 | 2016-11-16 | Saudi Basic Industries Corporation | Modified preformation method for catalyst activation in ethylene reactions |
KR101646178B1 (ko) * | 2014-11-25 | 2016-08-05 | 롯데케미칼 주식회사 | 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101645611B1 (ko) * | 2014-11-26 | 2016-08-05 | 롯데케미칼 주식회사 | 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101679515B1 (ko) * | 2015-02-12 | 2016-11-24 | 주식회사 엘지화학 | 올리고머화 촉매계의 제조방법 및 이에 의해 제조된 올리고머화 촉매계 |
EP3243847B1 (en) * | 2015-05-15 | 2020-08-26 | LG Chem, Ltd. | Catalytic composition and method of preparing polyolefin using same |
KR101768194B1 (ko) | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
KR101757835B1 (ko) | 2015-06-12 | 2017-07-13 | 주식회사 엘지화학 | 리간드 화합물, 유기 크롬 화합물, 올레핀 올리고머화용 촉매 시스템, 및 이를 이용한 올레핀의 올리고머화 방법 |
US10407359B2 (en) * | 2015-09-16 | 2019-09-10 | Sabic Global Technologies B.V. | Process for deactivation of an olefin oligomerization catalyst |
EP3394011B1 (en) | 2015-12-22 | 2020-07-22 | SABIC Global Technologies B.V. | Methods for toluene recovery from linear alpha olefin production |
KR101818180B1 (ko) * | 2016-05-13 | 2018-02-21 | 한국화학연구원 | 에틸렌 올리고머화 방법 |
RU2749592C2 (ru) * | 2016-12-30 | 2021-06-15 | Сабик Глобал Текнолоджис Б.В. | Способ получения раствора катализатора для селективного производства 1-гексена |
KR102472153B1 (ko) | 2016-12-30 | 2022-11-28 | 사빅 글로벌 테크놀러지스 비.브이. | 선택적인 1-헥센 제조용 균질 촉매의 제조 방법 |
WO2019074304A1 (ko) * | 2017-10-11 | 2019-04-18 | 롯데케미칼 주식회사 | 올레핀 올리고머화용 촉매계 및 이를 이용하는 올레핀 올리고머 제조방법 |
KR20210116515A (ko) | 2019-01-15 | 2021-09-27 | 차이나 페트로리움 앤드 케미컬 코포레이션 | 할로겐 함유 화합물 및 용도 및 촉매 조성물 및 에틸렌 올리고머화 방법 및 에틸렌 삼량체화 방법 및 에틸렌 사량체화 방법 |
CN110479382B (zh) * | 2019-08-19 | 2022-04-29 | 迈瑞尔实验设备(上海)有限公司 | 一种用于乙烯选择性齐聚制1-辛烯的催化剂体系及其制备方法与应用 |
US11440857B2 (en) | 2020-11-30 | 2022-09-13 | Saudi Arabian Oil Company | Catalyst systems |
US11623208B2 (en) | 2020-11-30 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems |
US11458463B2 (en) | 2020-11-30 | 2022-10-04 | Saudi Arabian Oil Company | Catalyst systems |
US11458462B2 (en) | 2020-11-30 | 2022-10-04 | Saudi Arabian Oil Company | Catalyst systems |
WO2022115748A1 (en) | 2020-11-30 | 2022-06-02 | Saudi Arabian Oil Company | Catalyst systems |
EP4294564A1 (en) | 2021-03-12 | 2023-12-27 | Saudi Arabian Oil Company | Catalyst systems |
US11484871B1 (en) | 2021-08-26 | 2022-11-01 | Saudi Arabian Oil Company | Catalyst systems |
CN114163475B (zh) * | 2021-12-01 | 2023-07-28 | 浙江智英石化技术有限公司 | 含吡咯基刚性结构多位点配体的催化剂体系、制备方法及应用 |
WO2023118226A1 (en) | 2021-12-23 | 2023-06-29 | Sabic Global Technologies B.V. | Catalyst composition for oligomerization reaction |
US11639321B1 (en) | 2022-08-31 | 2023-05-02 | Saudi Arabian Oil Company | Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands |
US11623901B1 (en) | 2022-08-31 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems that include silyl ether moieties |
WO2024047612A1 (en) | 2022-09-02 | 2024-03-07 | Sabic Global Technologies B.V. | Methods for producing 1-hexene |
US12037301B1 (en) | 2022-12-20 | 2024-07-16 | King Fahd University Of Petroleum And Minerals | Chromium-catalyzed ethylene oligomerization with bulky functionalized N-aryl bisphosphineamine ligands |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5259939A (en) | 1991-08-30 | 1993-11-09 | Beckman Instruments, Inc. | Capillary electrophoresis buffer |
US5811618A (en) * | 1991-10-16 | 1998-09-22 | Amoco Corporation | Ethylene trimerization |
GB9517105D0 (en) * | 1995-08-21 | 1995-10-25 | Bp Chem Int Ltd | Catalyst compositions |
ES2216137T3 (es) * | 1996-04-04 | 2004-10-16 | Bp Chemicals Limited | Un compuesto que puede utilizarse en una composicion catalitica. |
US6337297B1 (en) * | 1998-10-12 | 2002-01-08 | Tosoh Corporation | Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst |
GB9918635D0 (en) * | 1999-08-06 | 1999-10-13 | Bp Chem Int Ltd | Polymerisation process |
GB0016895D0 (en) * | 2000-07-11 | 2000-08-30 | Bp Chem Int Ltd | Olefin oligomerisation |
US7300904B2 (en) | 2001-12-20 | 2007-11-27 | Sasol Technology (Pty) Ltd. | Trimerisation and oligomerisation of olefins using a chromium based catalyst |
US7297832B2 (en) | 2002-12-20 | 2007-11-20 | Sasol Technology (Pty) Limited | Tetramerization of olefins |
CA2510190C (en) | 2002-12-20 | 2011-10-11 | Sasol Technology (Pty) Limited | Trimerisation of olefins |
US7273959B2 (en) | 2003-10-10 | 2007-09-25 | Shell Oil Company | Catalytic trimerization of olefinic monomers |
KR20080080570A (ko) * | 2005-11-21 | 2008-09-04 | 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 | 올레핀 단량체의 올리고머화를 위한 촉매법 |
CN100386149C (zh) * | 2006-06-26 | 2008-05-07 | 中国石油天然气股份有限公司 | 一种乙烯三聚催化剂及其应用 |
DE102009027375A1 (de) | 2009-07-01 | 2011-03-10 | Robert Bosch Gmbh | Diagnoseverfahren zum Durchführen einer Diagnose eines Systems |
-
2008
- 2008-06-16 US US12/452,594 patent/US8637721B2/en active Active
- 2008-06-16 WO PCT/EP2008/004815 patent/WO2009006979A2/en active Application Filing
- 2008-06-16 SG SG2012050308A patent/SG183005A1/en unknown
- 2008-06-16 CA CA2692533A patent/CA2692533C/en not_active Expired - Fee Related
- 2008-06-16 EP EP08773451A patent/EP2167231B8/en active Active
- 2008-06-16 ES ES08773451T patent/ES2394866T3/es active Active
- 2008-06-16 JP JP2010515362A patent/JP5158726B2/ja active Active
- 2008-06-16 KR KR1020107002616A patent/KR101241656B1/ko active IP Right Grant
- 2008-06-16 RU RU2010104668/04A patent/RU2456078C2/ru active
- 2008-06-16 BR BRPI0813779-0A patent/BRPI0813779B1/pt not_active IP Right Cessation
- 2008-06-16 MY MYPI20095649A patent/MY148675A/en unknown
- 2008-06-16 CN CN2008800229456A patent/CN101720253B/zh active Active
- 2008-06-20 TW TW097123207A patent/TWI415683B/zh not_active IP Right Cessation
-
2013
- 2013-12-20 US US14/135,674 patent/US9555404B2/en active Active
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102451758A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN102451759B (zh) * | 2010-10-22 | 2015-09-09 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN102451758B (zh) * | 2010-10-22 | 2015-12-16 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN102451759A (zh) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | 乙烯四聚催化剂、其制备和应用 |
CN103100420A (zh) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | 用于乙烯四聚的催化剂组合物及其中配体的制备方法 |
CN104511311A (zh) * | 2013-09-30 | 2015-04-15 | 华东理工大学 | 一种高选择性的乙烯三聚、四聚催化剂体系及其使用方法 |
CN104511311B (zh) * | 2013-09-30 | 2017-07-07 | 华东理工大学 | 一种高选择性的乙烯三聚、四聚催化剂体系及其使用方法 |
CN106573236A (zh) * | 2014-07-24 | 2017-04-19 | 沙特基础工业全球技术有限公司 | 用于乙烯的低聚以产生1‑己烯和/或1‑辛烯的催化剂组合物和方法 |
CN106573236B (zh) * | 2014-07-24 | 2020-05-29 | 沙特基础工业全球技术有限公司 | 用于乙烯的低聚以产生1-己烯和/或1-辛烯的催化剂组合物和方法 |
CN109289928A (zh) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | 一种用于乙烯齐聚的催化剂及其制备方法 |
CN113260457A (zh) * | 2018-11-12 | 2021-08-13 | 沙特基础全球技术有限公司 | 用于铬辅助乙烯低聚工艺中生产1-己烯的配体 |
CN113260457B (zh) * | 2018-11-12 | 2024-04-02 | 沙特基础全球技术有限公司 | 用于铬辅助乙烯低聚工艺中生产1-己烯的配体 |
CN111434670A (zh) * | 2019-01-15 | 2020-07-21 | 中国石油化工股份有限公司 | 含氟化合物及用途和乙烯齐聚催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
CN111434670B (zh) * | 2019-01-15 | 2021-07-30 | 中国石油化工股份有限公司 | 含氟化合物及用途和乙烯齐聚催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
CN111434668B (zh) * | 2019-01-15 | 2021-08-03 | 中国石油化工股份有限公司 | 含卤素化合物及用途和催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
WO2020147372A1 (zh) * | 2019-01-15 | 2020-07-23 | 中国石油化工股份有限公司 | 含卤素化合物及其作为催化剂配体在乙烯齐聚中的用途 |
CN111434668A (zh) * | 2019-01-15 | 2020-07-21 | 中国石油化工股份有限公司 | 含卤素化合物及用途和催化剂组合物及乙烯齐聚方法和乙烯三聚方法和乙烯四聚方法 |
CN111889142A (zh) * | 2020-07-23 | 2020-11-06 | 天津科技大学 | 一种乙烯选择性齐聚的催化剂体系、反应方法及其应用 |
CN111889142B (zh) * | 2020-07-23 | 2023-02-07 | 天津科技大学 | 一种乙烯选择性齐聚的催化剂体系、反应方法及其应用 |
CN112473741A (zh) * | 2020-10-22 | 2021-03-12 | 杭州小菱科技有限公司 | 一种乙烯齐聚催化剂体系及其制备方法与用途 |
CN112473741B (zh) * | 2020-10-22 | 2023-09-01 | 杭州小菱科技有限公司 | 一种乙烯齐聚催化剂体系及其制备方法与用途 |
JP2022104240A (ja) * | 2020-12-28 | 2022-07-08 | 株式会社アビー | 細胞凍結保存液、及び細胞凍結方法 |
JP7280623B2 (ja) | 2020-12-28 | 2023-05-24 | 株式会社アビー | 細胞凍結保存液、及び細胞凍結方法 |
Also Published As
Publication number | Publication date |
---|---|
BRPI0813779B1 (pt) | 2018-06-26 |
RU2456078C2 (ru) | 2012-07-20 |
CA2692533A1 (en) | 2009-01-15 |
JP2010532711A (ja) | 2010-10-14 |
WO2009006979A2 (en) | 2009-01-15 |
EP2167231A2 (en) | 2010-03-31 |
EP2167231B8 (en) | 2013-03-06 |
WO2009006979A3 (en) | 2009-03-26 |
SG183005A1 (en) | 2012-08-30 |
CN101720253B (zh) | 2013-07-17 |
MY148675A (en) | 2013-05-31 |
TWI415683B (zh) | 2013-11-21 |
BRPI0813779A2 (pt) | 2014-12-30 |
US9555404B2 (en) | 2017-01-31 |
RU2010104668A (ru) | 2011-08-20 |
ES2394866T3 (es) | 2013-02-06 |
CA2692533C (en) | 2013-03-05 |
KR101241656B1 (ko) | 2013-03-11 |
US20100190939A1 (en) | 2010-07-29 |
US20140179970A1 (en) | 2014-06-26 |
JP5158726B2 (ja) | 2013-03-06 |
TW200909055A (en) | 2009-03-01 |
US8637721B2 (en) | 2014-01-28 |
KR20100046170A (ko) | 2010-05-06 |
EP2167231B1 (en) | 2012-09-26 |
WO2009006979A8 (en) | 2009-12-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101720253B (zh) | 用于乙烯二聚、三聚和/或四聚的催化剂组合物和方法 | |
US9018431B2 (en) | Catalyst composition and process for oligomerization of ethylene | |
CA2703021C (en) | Catalyst composition and process for oligomerization of ethylene | |
CA2718804C (en) | Catalyst for oligomerization of ethylene, method for preparation thereof and process for oligomerization using it | |
JP2012523306A5 (zh) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |