CA2692533A1 - Catalyst composition and process for di-, tri- and/or tetramerization of ethylene - Google Patents
Catalyst composition and process for di-, tri- and/or tetramerization of ethylene Download PDFInfo
- Publication number
- CA2692533A1 CA2692533A1 CA 2692533 CA2692533A CA2692533A1 CA 2692533 A1 CA2692533 A1 CA 2692533A1 CA 2692533 CA2692533 CA 2692533 CA 2692533 A CA2692533 A CA 2692533A CA 2692533 A1 CA2692533 A1 CA 2692533A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst composition
- composition according
- catalyst
- ligand
- ethylene
- 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
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 System
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids R2=P—OH; Thiophosphinous acids; Aminophosphines R2-P-NH2 including R2P(=O)H; 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); 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 System
- 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 System
- 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
Abstract
The present invention relates to a catalyst composition and a process for di-, tri- and/or tetramerization of ethylene, wherein the catalyst composition comprises a chromium compound, a ligand of the general structure (A)R1R2P-N(R3)-P(R4)--N(R5)-H
or (B)R1R2P-N(R3-P(R4)-N(R5)-PR6R7, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP -unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution and a co-catalyst or activator.
or (B)R1R2P-N(R3-P(R4)-N(R5)-PR6R7, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP -unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution and a co-catalyst or activator.
Description
CATALYST COMPOSITION AND PROCESS FOR DI-, TRI- AND/OR
TETRAMERIZATION OF ETHYLENE
The present invention relates to a catalyst composition and a process for the di-, tri- and/or tetramerization of ethylene.
Existing processes for the production of linear alpha olefins (LAOs),including comonomer-grade 1-hexene and 1-octene, rely on the oligomerization of ethylene. These processes have in common that they lead to a product distribution of ethylene-oligomers of chain length 4, 6, 8 and so on. This is due to a chemical mechanism which is widely governed by competing chain growth- and displacement reaction steps, leading to a Schulz-Flory- or Poisson- product distribution.
From the marketing point of view, this product distribution poses a formidable challenge for the full-range alpha olefins producer. The reason is that each market segment served exhibits a very different behavior in terms of market size and growth, geography, fragmentation etc. It is, therefore, very difficult for the producer to adapt to the market requirements since part of the product spectrum might be in high demand in a given economic context, while at the same time other product cuts might not be marketable at all or only in a marginal niche. Currently, the highest-value LAO product is comonomer-grade 1 -hexene for the polymer industry, while 1-octene demand is also growing at a considerable rate.
Thus, the on-purpose production of the most economically viable LAOs, i.e.
comonomer-grade 1-hexene and 1-octene, appears highly desirable. To meet the requirements regarding high C6- and/or C8- selectivities, new processes have been developed. The only known selec-tive C6- commercial process has been commissioned by Chevron Phillips, see for a compre-hensive review e.g. J.T. Dixon, M.J. Green, F.M. Hess, D.H. Morgan, "Advances in selective ethylene trimerisation - a critical overview", Journal of Organometallic Chemistry 689 (2004) 3641-3668.
Furthermore, patent applications have been filed by Sasol (WO 93/053891 Al), disclosing chromium-based selective ethylene-trimerization catalyst systems, typically of the type CrC13(bis-(2-diphenylphosphino-ethyl)amine)/ MAO(methylaluminoxane). Also disclosed were variations of the ligand structure (e.g. bis(2-diethylphosphino-ethyl)-amine, pentame-thyldiethylenetriamine etc.). However, all these complexes generate considerable amounts of unwanted side products such as LAOs other than 1-hexene and polyethylene.
A large body of scientific publications and patent literature describes the use of chromium-based metal-organic complexes with ligands featuring the basic PNP-structure (for example bis(diphenylphosphino)amine-ligands) (D. S. McGuinness, P. Wasserscheid, W.
Keim, C. Hu, U. Englert, J.T. Dixon, C. Grove, "Novel Cr-PNP complexes as catalysts 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, "Highly selective chromium-based ethylene trimerisation catalysts with bulky diphosphinoamine 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 tetramerisation catalysts with polar-substituted diphosphinoamine ligands", Chem. Com-mun., 2005, 622-624; A. Jabri, P. Crewdson, S. Gambarotta, I. Korobkov, R.
Duchateau, "Iso-lation of a Cationic Chromium(II) Species in a Catalytic System for Ethylene Tri- and Tetramerization", Organometallics 2006, 25, 715-718; T. Agapie, S. J. Schofer, J. A. Labin-ger, J.E. Bercaw, "Mechanistic Studies of the Ethylene Trimerization Reaction with Chro-mium-Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metalla-cyclic 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 on Chro-mium Complexes with a Nitrogen-Bridged Diphosphine Ligand Having 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 System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents", Organometallics 2006, 25, 2733-2742; P. R. Elowe, C. McCann, P. G. Pringle, S. K. Spitzmesser, J. E.
Bercaw, "Ni-trogen-Linked Diphosphine Ligands with Ethers Attached to Nitrogen for Chromium-Catalyzed Ethylene Tri- and Tetramerization", Organometallics 2006, 25, 5255-5260; WO
2004/056578, WO 2004/056479, EP 02 794 480.0, EP 02 794 479.2; or the SNS-structure (D.
S. McGuinness, D. B. Brown, R. P. Tooze, F. M. Hess, J. T. Dixon, A. M. Z.
Slavin, "Ethyl-ene Trimerization with Cr-PNP and Cr-SNS Complexes: Effect of Ligand Structure, Metal
TETRAMERIZATION OF ETHYLENE
The present invention relates to a catalyst composition and a process for the di-, tri- and/or tetramerization of ethylene.
Existing processes for the production of linear alpha olefins (LAOs),including comonomer-grade 1-hexene and 1-octene, rely on the oligomerization of ethylene. These processes have in common that they lead to a product distribution of ethylene-oligomers of chain length 4, 6, 8 and so on. This is due to a chemical mechanism which is widely governed by competing chain growth- and displacement reaction steps, leading to a Schulz-Flory- or Poisson- product distribution.
From the marketing point of view, this product distribution poses a formidable challenge for the full-range alpha olefins producer. The reason is that each market segment served exhibits a very different behavior in terms of market size and growth, geography, fragmentation etc. It is, therefore, very difficult for the producer to adapt to the market requirements since part of the product spectrum might be in high demand in a given economic context, while at the same time other product cuts might not be marketable at all or only in a marginal niche. Currently, the highest-value LAO product is comonomer-grade 1 -hexene for the polymer industry, while 1-octene demand is also growing at a considerable rate.
Thus, the on-purpose production of the most economically viable LAOs, i.e.
comonomer-grade 1-hexene and 1-octene, appears highly desirable. To meet the requirements regarding high C6- and/or C8- selectivities, new processes have been developed. The only known selec-tive C6- commercial process has been commissioned by Chevron Phillips, see for a compre-hensive review e.g. J.T. Dixon, M.J. Green, F.M. Hess, D.H. Morgan, "Advances in selective ethylene trimerisation - a critical overview", Journal of Organometallic Chemistry 689 (2004) 3641-3668.
Furthermore, patent applications have been filed by Sasol (WO 93/053891 Al), disclosing chromium-based selective ethylene-trimerization catalyst systems, typically of the type CrC13(bis-(2-diphenylphosphino-ethyl)amine)/ MAO(methylaluminoxane). Also disclosed were variations of the ligand structure (e.g. bis(2-diethylphosphino-ethyl)-amine, pentame-thyldiethylenetriamine etc.). However, all these complexes generate considerable amounts of unwanted side products such as LAOs other than 1-hexene and polyethylene.
A large body of scientific publications and patent literature describes the use of chromium-based metal-organic complexes with ligands featuring the basic PNP-structure (for example bis(diphenylphosphino)amine-ligands) (D. S. McGuinness, P. Wasserscheid, W.
Keim, C. Hu, U. Englert, J.T. Dixon, C. Grove, "Novel Cr-PNP complexes as catalysts 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, "Highly selective chromium-based ethylene trimerisation catalysts with bulky diphosphinoamine 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 tetramerisation catalysts with polar-substituted diphosphinoamine ligands", Chem. Com-mun., 2005, 622-624; A. Jabri, P. Crewdson, S. Gambarotta, I. Korobkov, R.
Duchateau, "Iso-lation of a Cationic Chromium(II) Species in a Catalytic System for Ethylene Tri- and Tetramerization", Organometallics 2006, 25, 715-718; T. Agapie, S. J. Schofer, J. A. Labin-ger, J.E. Bercaw, "Mechanistic Studies of the Ethylene Trimerization Reaction with Chro-mium-Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metalla-cyclic 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 on Chro-mium Complexes with a Nitrogen-Bridged Diphosphine Ligand Having 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 System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents", Organometallics 2006, 25, 2733-2742; P. R. Elowe, C. McCann, P. G. Pringle, S. K. Spitzmesser, J. E.
Bercaw, "Ni-trogen-Linked Diphosphine Ligands with Ethers Attached to Nitrogen for Chromium-Catalyzed Ethylene Tri- and Tetramerization", Organometallics 2006, 25, 5255-5260; WO
2004/056578, WO 2004/056479, EP 02 794 480.0, EP 02 794 479.2; or the SNS-structure (D.
S. McGuinness, D. B. Brown, R. P. Tooze, F. M. Hess, J. T. Dixon, A. M. Z.
Slavin, "Ethyl-ene Trimerization with Cr-PNP and Cr-SNS Complexes: Effect of Ligand Structure, Metal
2 Oxidation State, and Role of Activator on Catalysis", Organometallics 2006, 25, 3605-3610;
A. Jabri, C. Temple, P. Crewdson, S. Gambarotta, I. Korobkov, R. Duchateau, "Role of the Metal 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: An Unan-ticipated Re-Oxidation Pathway", Angew. Chem. Int. Ed. 2006, 45, 7050-7053);
for both, trimerization and tetramerization of ethylene. Excess amounts of MAO are most commonly used as activator/co-catalyst.
While the majority of the published studies rely on Cr-PNP complexes, some deal with other ligands, e.g. of the general formula (R1)(R2)P-X-P(R3)(R4), where X is a bivalent organic bridging group, see WO 2005/039758 Al, or deal with entirely different complexes, such as titanocenes (H. Hagen, W.P. Kretschmer, F.R. van Buren, B. Hessen, D.A. van Oeffelen, "Se-lective ethylene trimerization: A study into the mechanism and the reduction of PE forma-tion", Journal of Molecular Catalysis A: Chemical 248 (2006) 237-247). In either case, the major concern is always selectivity and minimization of polyethylene formation.
The ethylene trimerization and tetramerization catalysts and processes disclosed so far in sci-entific and patent literature generally have one or more of the following disadvantages:
= Low selectivities to the desired products 1-hexene and/or 1-octene (undesired by-products from side reaction channels).
= Limited purities of the products, i.e. the selectivities within the specific C6- or C8-cut (isomerization, branched olefin formation etc.).
= Wax formation, i.e. formation of heavy, long-chain, high carbon - number products.
= Polymer formation (polyethylene, branched and/or cross-linked PE); this leads to con-siderable product yield loss and fouling of equipment.
A. Jabri, C. Temple, P. Crewdson, S. Gambarotta, I. Korobkov, R. Duchateau, "Role of the Metal 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: An Unan-ticipated Re-Oxidation Pathway", Angew. Chem. Int. Ed. 2006, 45, 7050-7053);
for both, trimerization and tetramerization of ethylene. Excess amounts of MAO are most commonly used as activator/co-catalyst.
While the majority of the published studies rely on Cr-PNP complexes, some deal with other ligands, e.g. of the general formula (R1)(R2)P-X-P(R3)(R4), where X is a bivalent organic bridging group, see WO 2005/039758 Al, or deal with entirely different complexes, such as titanocenes (H. Hagen, W.P. Kretschmer, F.R. van Buren, B. Hessen, D.A. van Oeffelen, "Se-lective ethylene trimerization: A study into the mechanism and the reduction of PE forma-tion", Journal of Molecular Catalysis A: Chemical 248 (2006) 237-247). In either case, the major concern is always selectivity and minimization of polyethylene formation.
The ethylene trimerization and tetramerization catalysts and processes disclosed so far in sci-entific and patent literature generally have one or more of the following disadvantages:
= Low selectivities to the desired products 1-hexene and/or 1-octene (undesired by-products from side reaction channels).
= Limited purities of the products, i.e. the selectivities within the specific C6- or C8-cut (isomerization, branched olefin formation etc.).
= Wax formation, i.e. formation of heavy, long-chain, high carbon - number products.
= Polymer formation (polyethylene, branched and/or cross-linked PE); this leads to con-siderable product yield loss and fouling of equipment.
3 = Poor turnover rates / catalyst activity, resulting in high cost per kg product.
= High catalyst- or ligand cost.
= Difficult ligand synthesis, resulting in poor availability and high catalyst cost.
= Susceptibility of catalyst performance, in terms of both activity and selectivity, to trace impurities (catalyst losses/-poisoning).
= Difficult handling of catalyst components in a technical environment (catalyst com-plex synthesis, pre-mixing, inertization, catalyst-or ligand recovery).
= Harsh reaction conditions, i.e. high temperatures and pressures, resulting in high in-vest-, maintenance-, and energy cost.
= High co-catalyst/activator cost and/or -consumption = Susceptibility to varying co-catalyst qualities; often the case when larger amounts of relatively ill-defined compounds must be used as activators (e.g. certain MAO-varieties).
It is an object of the present invention to provide a catalyst composition and a process for se-lective di-, tri- and/or tetramerization of ethylene overcoming the disadvantages of the prior art. Especially, higher selectivities shall be achieved with avoidance of formation of consider-able amounts of waxes and polymers, regardless of the process conditions.
Further, the cata-lyst composition shall also provide sufficiently high activity turnover frequency for a techni-cal process.
= High catalyst- or ligand cost.
= Difficult ligand synthesis, resulting in poor availability and high catalyst cost.
= Susceptibility of catalyst performance, in terms of both activity and selectivity, to trace impurities (catalyst losses/-poisoning).
= Difficult handling of catalyst components in a technical environment (catalyst com-plex synthesis, pre-mixing, inertization, catalyst-or ligand recovery).
= Harsh reaction conditions, i.e. high temperatures and pressures, resulting in high in-vest-, maintenance-, and energy cost.
= High co-catalyst/activator cost and/or -consumption = Susceptibility to varying co-catalyst qualities; often the case when larger amounts of relatively ill-defined compounds must be used as activators (e.g. certain MAO-varieties).
It is an object of the present invention to provide a catalyst composition and a process for se-lective di-, tri- and/or tetramerization of ethylene overcoming the disadvantages of the prior art. Especially, higher selectivities shall be achieved with avoidance of formation of consider-able amounts of waxes and polymers, regardless of the process conditions.
Further, the cata-lyst composition shall also provide sufficiently high activity turnover frequency for a techni-cal process.
4 In other words, the broad spectrum of LAO (linear alpha olefins) products in prior art proc-esses shall be avoided and the selective production of preferably the economically most de-sired product, 1-hexene, shall be allowed. Depending on the nature of the co-catalyst and the reaction conditions, also the co-production of, e.g. 1-butene and 1-hexene, and 1-hexene and 1-octene, respectively, shall be provided.
The object is achieved by a catalyst composition comprising:
(a) a chromium compound;
(b) a ligand of the general structure (A) RiR2P-N(R3)-P(R4)-N(R5)-H or (B) RIRZP-N(R3)-P(R4)-N(R5)-PR6R7 wherein Ri, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, CI-Cio-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
(c) an activator or co-catalyst.
As is to be understood, any cyclic derivatives of (A) and (B) can be utilized as ligand, wherein at least one of the P or N atoms of the PNPN-unit (structure (A)) or PNPNP-unit (structure (B)) is a ring member, the ring being formed from one or more constituent com-pounds of structures (A) or (B) by substitution, i. e. by formally eliminating per constituent compound either two whole groups Rl-R7 (as defined) or H, one atom from each of two groups Ri-R7 (as defined) or a whole group Ri-R7 (as defined) or H and an atom from another group RI-R7 (as defined), and joining the formally so-created valence-unsaturated sites by one covalent bond per constituent compound to provide the same valence as initially present at a given site.
Suitable cyclic derivatives of (A) and (B) can be as follows:
N N
R1-P ~P- H R1-P~ 1-11, P-R4 H
p R1 \ P%
P H
Preferably, the chromium compound is selected from organic or inorganic salts, coordination complexes and organometallic complexes of Cr(II) or Cr(III).
Most preferably, the chromium compound is selected from CrC13(THF)3, Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate and (benzene)tricarbonyl-chromium.
It is also preferred that R1, R2, R3, R4, R5, R6 and R7 are selected from chloro, amino, trimethyl-silyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, tolyl and xylyl.
Suitable ligands (A) and (B) having an amino-substituent can be as follows:
H
N
PhN/
Ih I PhPNPNN
HN I
Ph Ph N
I H
Ph~P/N'__1 P~NN
Jh Ih I
In one embodiment, the activator or co-catalyst is selected from trimethylaluminum, triethy-laluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminumsesquichloride, di-ethylaluminum chloride, ethylaluminumdichloride, methylaluminoxane (MAO) or mixtures thereof.
Most preferred, the ligand is selected from (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(tert-butyl)-H and (Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H.
A catalyst composition is also preferably provided comprising a solvent.
Preferably, the solvent is selected from aromatic hydrocarbons, straight-chain and cyclic ali-phatic hydrocarbons, straight-chain olefins and ethers, preferably toluene, benzene, ethylben-zene, cumene, xylenes, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethylether or tetrahydrofurane, most preferably toluene.
Any mixture of these solvents may be used as well.
In one embodiment, the concentration of the chromium compound is from 0.01 to mmol/l, preferably 0.1 to 10 mmol/1.
The ligand/Cr ratio is preferably from 0.5 to 50, preferably 0.8 to 2Ø
The Al/Cr ratio is preferably from 1 to 1000, preferably 10 to 200.
As is obvious for someone skilled in the art, the components (a) to (c) for providing the cata-lyst composition are more or less considered as starting materials, but may be converted when the three compounds (a)-(c) are mixed to form the catalyst composition. In this regard the catalyst composition according to the present invention can be also illustrated as being ob-tainable by combining at least:
(a) a chromium compound;
(b) a ligand of the general structure (A) RIRZP-N(R3)-P(R4)-N(R5)-H or (B) RiR2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein RI, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, Cl-Clo-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
According to the invention is also a process for di-, tri- and/or tetramerization of ethylene, comprising subjecting a catalyst composition of the invention to a gas phase of ethylene in a reactor and conducting an oligomerization.
Preferably, the oligomerization is carried out at a pressure of 1 to 200 bar, preferably 10 to 50 bar.
Also preferred, the oligomerization is carried out at a temperature of from 10 to 200 C, pref-erably 20 to 100 C.
In one embodiment, the process is carried out continuously, semi-continuously or discontinu-ously.
The mean residence time may be from 10 minutes to 20 hours, preferably 1 to 4 hours.
When combining the ligand according to general structure (A) and a co-catalyst, a reaction product can be obtained having the structural formula.
R3 P~"~ R5 N/ N
P
or P
N / N \
R3 p P R3 N N /
p R5 The reaction product disclosed above can, of course, be utilized in the catalyst composition instead of the separate addition of ligand and co-catalyst and shall be also within the scope of protection.
Under reaction conditions, the PNPN-H-type ligands are deprotonated in-situ by the co-catalyst. In a further advantageous embodiment of the present invention, the active catalyst species can be also formed ex-situ, by a separate deprotonation/elimination-step leading to the structures given above.
Especially, if smaller or sterically less demanding groups Ri-R7 are used, the ligands tend to form dimers. These dimeric cyclodiphosphazanes can directly be used to form the active cata-lyst species.
The general ligand structures (A) and (B) as disclosed can be also illustrated by the following structural formula:
R3 p R5 N N
P H
R3 p R5 N N
P
/P\ \
Most preferred ligand structures are (Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H and P I /
N/
I I
P H
\ ~ \
and \
I /
N P N
I
P
I \ I \
and P
N N
P H
Surprisingly, it was found that with the inventive catalyst composition and the process for di-, tri- and tetramerization of ethylene the disadvantages of the prior art can be significantly overcome. Especially, the inventive process and the catalyst composition allows the produc-tion of 1-hexene with high turnover rate and selectivity. Further, high reproducibility is ob-tained, i.e. the catalyst composition is stable against interference from impurities and fluctua-tions in process conditions. Expensive co-catalysts, such as MAO, can be totally or to a large extent replaced by cheaper substances, preferably by triethylaluminium.
Additionally, co-catalysts which are prone to quality instabilities, due to their relatively poor definition of chemical structure (e.g. MAO), are partly or totally replaced by well-defined chemical species (triethyl aluminium). With the inventive process no wide LAO product distribution is ob-tained, but specific alpha-olefins can be selectively produced. Further, the polymer formation is suppressed very well. Moreover, mild reaction conditions can be chosen, resulting conse-quently in low invest costs for technical-scale plant and low energy and operation costs. Addi-tionally, a relatively simple, straight-forward process design is possible.
Very high 1-hexene or 1-hexene/1-octene-selectivities lead to high product purities without additional purification steps in the separation train.
Further advantages and features of the present invention are now illustrated in the following examples section with reference to the accompanying drawing, wherein figure 1 is a GC/FID
analysis of the liquid phase obtained in example 2.
The active catalyst may be prepared by combining the chromium source and the ligand in a suitable solvent, preferentially toluene, such that the chromium concentration is 0.01 to 100 mmol/l, preferentially between 0.1 and 10 mmol/1 and the ligand/Cr - ratio is 0.5 to 50 mol/mol, preferentially between 0.8 and 2.0 mol/mol. The co-catalyst, preferentially triethy-laluminum or any mixture of triethylaluminum and MAO or triethylaluminum and trimethy-laluminum, is added as a solution in toluene, so as to result in an Al/Cr -ratio between 1 and 1000 mol/mol. The preferred Al/Cr - ratio is 10 to 200 mol/mol.
The solvent toluene can be replaced by other solvents such as aromatic hydrocarbons other than toluene (benzene, ethylbenzene, cumenene, xylenes, mesitylene etc.), aliphatic hydrocar-bons (both straight-chain and cyclic, e.c hexane, octane, cyclohexane), straight-chain olefins like hexene, heptene, octene etc. or ethers like, for example diethylether or tetrahydrofurane.
The catalyst solution is then subjected to a gas phase of dry ethylene at pressures between 1 and 200 bar, preferentially 10 and 50 bar in a suitable pressure reactor. The reactor can be of any kind suitable to provide sufficient contact between gas- and liquid phase, such as bubble column reactors, stirred tank reactors, flow reactors with fixed or distributed ethylene-injection and the like.
Preferred reaction temperatures are between 10 and 200 C, the most preferred temperature regime is 20 to 100 C. Mean residence times and residence time distributions (in case of a continuous process) are chosen so as to achieve sufficient conversion at high selectivities.
Typical mean residence times are between 10 minutes and 20 hours (depending on tempera-ture and pressure). The preferred range is 1 to 4 hours.
Example 1: Ligand Preparation 1.1 Preparation of Bis(isopropyl-amino)-phenylphosphine (NPN) To a stirred solution of isopropylamine (30m1, 352 mmol) in diethylether (250 ml), dichloro-phenylphosphine (9.63 ml, 71mmo1, dissolved in 50m1 diethylether) was added at 0 C over a period of 30 min. After stirring for a total of 72 hrs the solution was filtrated. The residue was washed with diethylether and the solvent was removed in vacuum. The remaining oil was distilled at 0.2 Torr/76-78 C to give a colorless liquid with 33% yield (5.3g). 31P{H} NMR:
49.0 ppm.
1.2 Preparation of (phenyl)2PN(isopropyl)P(phenyl)NH(isopropyl) (PNPN-H) A solution of the NPN-species (as prepared in section 1.1)(2.4g, 10.7mmol) in tetrahydrofu-rane (10ml) was added dropwise to a stirred solution of triethylamine (6ml) and chlorodi-phenylphosphine (2.36g, 10.7mmol) in thf (40ml) at -40 C. After additional stirring for 24h hrs at room temperature the triethylammonium salt was filtrated off and the residue was dis-solved in n-hexane, filtrated again, and the solution was kept at -30 C for crystallisation.
Yield 52% (2.3g, 5.6mmol). 31P{H} NMR: 41.2, 68.4 (broad).
Example 2: Ethylene Trimerization A 300 ml pressure reactor, equipped with dip tube, thermowell, gas entrainment stirrer, cool-ing coil, control units for temperature, pressure, and stirrer speed (all hooked up to a data ac-quisition system) was inertized with dry argon and filled with 100 ml anhydrous toluene.
1694 l of a 4.017 wt% - solution of the ligand 1 ((phenyl)2PN(isopropyl)P(phenyl)NH(isopropyl)) in toluene was combined with 59.2 mg CrC13(thf)3 (thf = tetrahydrofurane) under an argon blanket. This catalyst solution was trans-ferred to the reactor under constant argon flow, along with 3.6 ml of a 1.9 mol/1 solution of triethylaluminum in toluene.
The chosen volumes and masses correspond to a chromium concentration of 1 mmol/1 at a ligand / CrC13(thf)3 ratio of 1.5 mol/mol and a Al/Cr ratio of 70 mol/mol.
The reactor was sealed, pressurized with 30 bar dry ethylene and heated to 40 C. While stir-ring at 1200 rpm, the ethylene consumption was monitored by the data acquisition system and an electronic balance by constantly weighing the ethylene pressure cylinder.
After 120 min residence time, the reaction in the liquid phase was quenched by transferring the liquid inven-tory by means of the ethylene pressure to a glass vessel filled with approx.
100 ml water. The entire gas phase from the reactor's head space was quantified by a calibrated gas meter and was then collected quantitatively in a purged and evacuated gas bag.
After separation of the liquid organic phase, the total mass was determined by weighing. Sub-sequently, the composition of the organic phase was analyzed by GC/FID. The previously collected gas phase was analyzed separately by GC/FID.
Based on the measured data, the mass balance was closed and the overall yields and selectivi-ties were determined.
For illustration, a GC-trace of the liquid phase is given in Fig. 1.
Surprisingly, a very high 1-hexene yield is observed, with only trace amounts of 1-butene, 1-octene, 1-decene and 1-dodecene. In repetitive experiments under clean and well-defined conditions, no discernible polymer formation was observed. The average C6-yield exceeds 89 wt% at 40 C
and de-grades slightly with increasing temperature. Even more surprising than the high C6-yields are the 1-hexene selectivities within the C6-fraction. At 40 C reaction temperature, the measured 1-hexene selectivities approach 100 wt%, i.e. are not distinguishable from 100 wt% within experimental error, thus rendering any polishing separation unit to ensure 1-hexene specifica-tions obsolete in technical operations. The novel catalyst system disclosed in this invention is capable of suppressing very effectively any unwanted side reaction channel, such as olefin isomerization or -rearrangement, Friedel-Crafts-alkylation of the solvent, co-oligomerization and the like.
A summary of typical results from a series of non-optimized experiments is given in table 1.
Higher temperatures, although causing deteriorating C6-yields, can, however, be useful for the co-production of C4- and C6-olefins, while still giving high 1-butene and 1-hexene selec-tivities (product purities) within the C4- and C6-fraction, respectively.
Table 1: Influence of temperature on C6-yields and 1-hexene selectivity (process pa-rameters other than temperature as specified in example 1) Temperature C4-Yield, wt% C6-Yield, wt% 1-Hexene Selectivity C in C6-Fraction, wt%
40 8.2 89 100 65 9.6 84 97 Using different co-catalysts and/or by varying the structure of the functional groups of the ligand or the Cr/ligand - ratio, the system can be switched from a pure 1-hexene, i.e. ethylene-trimerization catalyst to a combined tri-/tetramerization system, producing 1-hexene and 1-octene with high selectivities.
With ligand 1, triethylaluminum as co-catalyst results in high 1-hexene yields, while MAO
leads to 1-hexene and 1-octene.
Combinations of co-catalysts, such as triethylaluminum spiked with small amounts of MAO
or trimethylaluminum, can increase the overall activity, i.e. the conversion rate, by a factor of at least three, while maintaining the high yields and selectivities.
Further preferred variations of the PNPN-H -structured basic ligand type were successfully synthesized and tested as shown above.
The features disclosed in the foregoing description, in the claims and in the drawing may, both separately and in any combination thereof, be material for realizing the invention in di-verse forms thereof.
The object is achieved by a catalyst composition comprising:
(a) a chromium compound;
(b) a ligand of the general structure (A) RiR2P-N(R3)-P(R4)-N(R5)-H or (B) RIRZP-N(R3)-P(R4)-N(R5)-PR6R7 wherein Ri, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, CI-Cio-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
(c) an activator or co-catalyst.
As is to be understood, any cyclic derivatives of (A) and (B) can be utilized as ligand, wherein at least one of the P or N atoms of the PNPN-unit (structure (A)) or PNPNP-unit (structure (B)) is a ring member, the ring being formed from one or more constituent com-pounds of structures (A) or (B) by substitution, i. e. by formally eliminating per constituent compound either two whole groups Rl-R7 (as defined) or H, one atom from each of two groups Ri-R7 (as defined) or a whole group Ri-R7 (as defined) or H and an atom from another group RI-R7 (as defined), and joining the formally so-created valence-unsaturated sites by one covalent bond per constituent compound to provide the same valence as initially present at a given site.
Suitable cyclic derivatives of (A) and (B) can be as follows:
N N
R1-P ~P- H R1-P~ 1-11, P-R4 H
p R1 \ P%
P H
Preferably, the chromium compound is selected from organic or inorganic salts, coordination complexes and organometallic complexes of Cr(II) or Cr(III).
Most preferably, the chromium compound is selected from CrC13(THF)3, Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate and (benzene)tricarbonyl-chromium.
It is also preferred that R1, R2, R3, R4, R5, R6 and R7 are selected from chloro, amino, trimethyl-silyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, tolyl and xylyl.
Suitable ligands (A) and (B) having an amino-substituent can be as follows:
H
N
PhN/
Ih I PhPNPNN
HN I
Ph Ph N
I H
Ph~P/N'__1 P~NN
Jh Ih I
In one embodiment, the activator or co-catalyst is selected from trimethylaluminum, triethy-laluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminumsesquichloride, di-ethylaluminum chloride, ethylaluminumdichloride, methylaluminoxane (MAO) or mixtures thereof.
Most preferred, the ligand is selected from (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(tert-butyl)-H and (Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H.
A catalyst composition is also preferably provided comprising a solvent.
Preferably, the solvent is selected from aromatic hydrocarbons, straight-chain and cyclic ali-phatic hydrocarbons, straight-chain olefins and ethers, preferably toluene, benzene, ethylben-zene, cumene, xylenes, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethylether or tetrahydrofurane, most preferably toluene.
Any mixture of these solvents may be used as well.
In one embodiment, the concentration of the chromium compound is from 0.01 to mmol/l, preferably 0.1 to 10 mmol/1.
The ligand/Cr ratio is preferably from 0.5 to 50, preferably 0.8 to 2Ø
The Al/Cr ratio is preferably from 1 to 1000, preferably 10 to 200.
As is obvious for someone skilled in the art, the components (a) to (c) for providing the cata-lyst composition are more or less considered as starting materials, but may be converted when the three compounds (a)-(c) are mixed to form the catalyst composition. In this regard the catalyst composition according to the present invention can be also illustrated as being ob-tainable by combining at least:
(a) a chromium compound;
(b) a ligand of the general structure (A) RIRZP-N(R3)-P(R4)-N(R5)-H or (B) RiR2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein RI, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, Cl-Clo-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
According to the invention is also a process for di-, tri- and/or tetramerization of ethylene, comprising subjecting a catalyst composition of the invention to a gas phase of ethylene in a reactor and conducting an oligomerization.
Preferably, the oligomerization is carried out at a pressure of 1 to 200 bar, preferably 10 to 50 bar.
Also preferred, the oligomerization is carried out at a temperature of from 10 to 200 C, pref-erably 20 to 100 C.
In one embodiment, the process is carried out continuously, semi-continuously or discontinu-ously.
The mean residence time may be from 10 minutes to 20 hours, preferably 1 to 4 hours.
When combining the ligand according to general structure (A) and a co-catalyst, a reaction product can be obtained having the structural formula.
R3 P~"~ R5 N/ N
P
or P
N / N \
R3 p P R3 N N /
p R5 The reaction product disclosed above can, of course, be utilized in the catalyst composition instead of the separate addition of ligand and co-catalyst and shall be also within the scope of protection.
Under reaction conditions, the PNPN-H-type ligands are deprotonated in-situ by the co-catalyst. In a further advantageous embodiment of the present invention, the active catalyst species can be also formed ex-situ, by a separate deprotonation/elimination-step leading to the structures given above.
Especially, if smaller or sterically less demanding groups Ri-R7 are used, the ligands tend to form dimers. These dimeric cyclodiphosphazanes can directly be used to form the active cata-lyst species.
The general ligand structures (A) and (B) as disclosed can be also illustrated by the following structural formula:
R3 p R5 N N
P H
R3 p R5 N N
P
/P\ \
Most preferred ligand structures are (Ph)2P-N(i-Pr)-P(Ph)-N(i-Pr)-H and P I /
N/
I I
P H
\ ~ \
and \
I /
N P N
I
P
I \ I \
and P
N N
P H
Surprisingly, it was found that with the inventive catalyst composition and the process for di-, tri- and tetramerization of ethylene the disadvantages of the prior art can be significantly overcome. Especially, the inventive process and the catalyst composition allows the produc-tion of 1-hexene with high turnover rate and selectivity. Further, high reproducibility is ob-tained, i.e. the catalyst composition is stable against interference from impurities and fluctua-tions in process conditions. Expensive co-catalysts, such as MAO, can be totally or to a large extent replaced by cheaper substances, preferably by triethylaluminium.
Additionally, co-catalysts which are prone to quality instabilities, due to their relatively poor definition of chemical structure (e.g. MAO), are partly or totally replaced by well-defined chemical species (triethyl aluminium). With the inventive process no wide LAO product distribution is ob-tained, but specific alpha-olefins can be selectively produced. Further, the polymer formation is suppressed very well. Moreover, mild reaction conditions can be chosen, resulting conse-quently in low invest costs for technical-scale plant and low energy and operation costs. Addi-tionally, a relatively simple, straight-forward process design is possible.
Very high 1-hexene or 1-hexene/1-octene-selectivities lead to high product purities without additional purification steps in the separation train.
Further advantages and features of the present invention are now illustrated in the following examples section with reference to the accompanying drawing, wherein figure 1 is a GC/FID
analysis of the liquid phase obtained in example 2.
The active catalyst may be prepared by combining the chromium source and the ligand in a suitable solvent, preferentially toluene, such that the chromium concentration is 0.01 to 100 mmol/l, preferentially between 0.1 and 10 mmol/1 and the ligand/Cr - ratio is 0.5 to 50 mol/mol, preferentially between 0.8 and 2.0 mol/mol. The co-catalyst, preferentially triethy-laluminum or any mixture of triethylaluminum and MAO or triethylaluminum and trimethy-laluminum, is added as a solution in toluene, so as to result in an Al/Cr -ratio between 1 and 1000 mol/mol. The preferred Al/Cr - ratio is 10 to 200 mol/mol.
The solvent toluene can be replaced by other solvents such as aromatic hydrocarbons other than toluene (benzene, ethylbenzene, cumenene, xylenes, mesitylene etc.), aliphatic hydrocar-bons (both straight-chain and cyclic, e.c hexane, octane, cyclohexane), straight-chain olefins like hexene, heptene, octene etc. or ethers like, for example diethylether or tetrahydrofurane.
The catalyst solution is then subjected to a gas phase of dry ethylene at pressures between 1 and 200 bar, preferentially 10 and 50 bar in a suitable pressure reactor. The reactor can be of any kind suitable to provide sufficient contact between gas- and liquid phase, such as bubble column reactors, stirred tank reactors, flow reactors with fixed or distributed ethylene-injection and the like.
Preferred reaction temperatures are between 10 and 200 C, the most preferred temperature regime is 20 to 100 C. Mean residence times and residence time distributions (in case of a continuous process) are chosen so as to achieve sufficient conversion at high selectivities.
Typical mean residence times are between 10 minutes and 20 hours (depending on tempera-ture and pressure). The preferred range is 1 to 4 hours.
Example 1: Ligand Preparation 1.1 Preparation of Bis(isopropyl-amino)-phenylphosphine (NPN) To a stirred solution of isopropylamine (30m1, 352 mmol) in diethylether (250 ml), dichloro-phenylphosphine (9.63 ml, 71mmo1, dissolved in 50m1 diethylether) was added at 0 C over a period of 30 min. After stirring for a total of 72 hrs the solution was filtrated. The residue was washed with diethylether and the solvent was removed in vacuum. The remaining oil was distilled at 0.2 Torr/76-78 C to give a colorless liquid with 33% yield (5.3g). 31P{H} NMR:
49.0 ppm.
1.2 Preparation of (phenyl)2PN(isopropyl)P(phenyl)NH(isopropyl) (PNPN-H) A solution of the NPN-species (as prepared in section 1.1)(2.4g, 10.7mmol) in tetrahydrofu-rane (10ml) was added dropwise to a stirred solution of triethylamine (6ml) and chlorodi-phenylphosphine (2.36g, 10.7mmol) in thf (40ml) at -40 C. After additional stirring for 24h hrs at room temperature the triethylammonium salt was filtrated off and the residue was dis-solved in n-hexane, filtrated again, and the solution was kept at -30 C for crystallisation.
Yield 52% (2.3g, 5.6mmol). 31P{H} NMR: 41.2, 68.4 (broad).
Example 2: Ethylene Trimerization A 300 ml pressure reactor, equipped with dip tube, thermowell, gas entrainment stirrer, cool-ing coil, control units for temperature, pressure, and stirrer speed (all hooked up to a data ac-quisition system) was inertized with dry argon and filled with 100 ml anhydrous toluene.
1694 l of a 4.017 wt% - solution of the ligand 1 ((phenyl)2PN(isopropyl)P(phenyl)NH(isopropyl)) in toluene was combined with 59.2 mg CrC13(thf)3 (thf = tetrahydrofurane) under an argon blanket. This catalyst solution was trans-ferred to the reactor under constant argon flow, along with 3.6 ml of a 1.9 mol/1 solution of triethylaluminum in toluene.
The chosen volumes and masses correspond to a chromium concentration of 1 mmol/1 at a ligand / CrC13(thf)3 ratio of 1.5 mol/mol and a Al/Cr ratio of 70 mol/mol.
The reactor was sealed, pressurized with 30 bar dry ethylene and heated to 40 C. While stir-ring at 1200 rpm, the ethylene consumption was monitored by the data acquisition system and an electronic balance by constantly weighing the ethylene pressure cylinder.
After 120 min residence time, the reaction in the liquid phase was quenched by transferring the liquid inven-tory by means of the ethylene pressure to a glass vessel filled with approx.
100 ml water. The entire gas phase from the reactor's head space was quantified by a calibrated gas meter and was then collected quantitatively in a purged and evacuated gas bag.
After separation of the liquid organic phase, the total mass was determined by weighing. Sub-sequently, the composition of the organic phase was analyzed by GC/FID. The previously collected gas phase was analyzed separately by GC/FID.
Based on the measured data, the mass balance was closed and the overall yields and selectivi-ties were determined.
For illustration, a GC-trace of the liquid phase is given in Fig. 1.
Surprisingly, a very high 1-hexene yield is observed, with only trace amounts of 1-butene, 1-octene, 1-decene and 1-dodecene. In repetitive experiments under clean and well-defined conditions, no discernible polymer formation was observed. The average C6-yield exceeds 89 wt% at 40 C
and de-grades slightly with increasing temperature. Even more surprising than the high C6-yields are the 1-hexene selectivities within the C6-fraction. At 40 C reaction temperature, the measured 1-hexene selectivities approach 100 wt%, i.e. are not distinguishable from 100 wt% within experimental error, thus rendering any polishing separation unit to ensure 1-hexene specifica-tions obsolete in technical operations. The novel catalyst system disclosed in this invention is capable of suppressing very effectively any unwanted side reaction channel, such as olefin isomerization or -rearrangement, Friedel-Crafts-alkylation of the solvent, co-oligomerization and the like.
A summary of typical results from a series of non-optimized experiments is given in table 1.
Higher temperatures, although causing deteriorating C6-yields, can, however, be useful for the co-production of C4- and C6-olefins, while still giving high 1-butene and 1-hexene selec-tivities (product purities) within the C4- and C6-fraction, respectively.
Table 1: Influence of temperature on C6-yields and 1-hexene selectivity (process pa-rameters other than temperature as specified in example 1) Temperature C4-Yield, wt% C6-Yield, wt% 1-Hexene Selectivity C in C6-Fraction, wt%
40 8.2 89 100 65 9.6 84 97 Using different co-catalysts and/or by varying the structure of the functional groups of the ligand or the Cr/ligand - ratio, the system can be switched from a pure 1-hexene, i.e. ethylene-trimerization catalyst to a combined tri-/tetramerization system, producing 1-hexene and 1-octene with high selectivities.
With ligand 1, triethylaluminum as co-catalyst results in high 1-hexene yields, while MAO
leads to 1-hexene and 1-octene.
Combinations of co-catalysts, such as triethylaluminum spiked with small amounts of MAO
or trimethylaluminum, can increase the overall activity, i.e. the conversion rate, by a factor of at least three, while maintaining the high yields and selectivities.
Further preferred variations of the PNPN-H -structured basic ligand type were successfully synthesized and tested as shown above.
The features disclosed in the foregoing description, in the claims and in the drawing may, both separately and in any combination thereof, be material for realizing the invention in di-verse forms thereof.
Claims (17)
1. Catalyst composition comprising:
(a) a chromium compound;
(b) a ligand of the general structure (A) R1R2P-N(R3)-P(R4)-N(R5)-H or (B) R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
(a) a chromium compound;
(b) a ligand of the general structure (A) R1R2P-N(R3)-P(R4)-N(R5)-H or (B) R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
2. Catalyst composition according to claim 1, wherein the chromium compound is se-lected from organic or inorganic salts, coordination complexes and organometallic complexes of Cr(II) or Cr(III).
3. Catalyst composition according to claim 2, wherein the chromium compound is se-lected from CrCl3(THF)3, Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacar-bonyl, Cr(III)-2-ethylhexanoate and (benzene)tricarbonyl-chromium.
4. Catalyst composition according to any of the preceding claims, wherein R1, R2, R3, R4, R5, R6 and R7 are selected from chloro, amino, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl, tolyl and xylyl.
5. Catalyst composition according to any of the preceding claims, wherein the activator or co-catalyst is selected from trimethylaluminum, triethylaluminum, triisopropylalu-minum, triisobutylaluminum, ethylaluminumsesquichloride, diethylaluminum chlo-ride, ethylaluminumdichloride, methylaluminoxane (MAO) or mixtures thereof.
6. Catalyst composition according to any of the preceding claims, wherein the ligand is selected from (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(tert-butyl)-H and (Ph)2P-N(i-Pr)-P(Ph)-N(CH(CH3)(Ph))-H.
7. Catalyst composition according to any of the preceding claims additionally comprising a solvent.
8. Catalyst composition according to claim 7, wherein the solvent is selected from aro-matic hydrocarbons, straight-chain and cyclic aliphatic hydrocarbons, straight-chain olefins and ethers, preferably toluene, benzene, ethylbenzene, cumene, xylenes, me-sitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethylether or tetrahydrofurane or mixtures thereof, most preferably toluene.
9. Catalyst composition according to claim 7 or 8, wherein the concentration of the chromium compound is from 0.01 to 100 mmol/1, preferably 0.1 to 10 mmol/1.
10. Catalyst composition according to any of the preceding claims, wherein the ligand/Cr ratio is from 0.5 to 50, preferably 0.8 to 2Ø
11. Catalyst composition according to claim 5, wherein the Al/Cr ratio is from 1:1 to 1000:1, preferably 10:1 to 200:1.
12. Catalyst composition, obtainable by combining at least:
(a) a chromium compound;
(b) a ligand of the general structure (A) R1R2P-N(R3)-P(R4)-N(R5)-H or (B) R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
(a) a chromium compound;
(b) a ligand of the general structure (A) R1R2P-N(R3)-P(R4)-N(R5)-H or (B) R1R2P-N(R3)-P(R4)-N(R5)-PR6R7, wherein R1, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10-alkyl, aryl and substituted aryl, or any cyclic de-rivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitu-tion;
and (c) an activator or co-catalyst.
13. Process for di-, tri- and/or tetramerization of ethylene, comprising subjecting a catalyst composition according to any of the claims 1 to 12 to a gas phase of ethylene in a re-actor and conducting an oligomerization.
14. Process according to claim 13, wherein the oligomerization is carried out at a pressure of 1 to 200 bar, preferably 10 to 50 bar.
15. Process according to claim 13 or 14, wherein the oligomerization is carried out at a temperature of from 10 to 200°C, preferably 20 to 100°C.
16. Process according to any of the claims 13 to 15, wherein the process is carried out continuously.
17. Process according to any of the claims 13 to 16, wherein the mean residence time is from 10 minutes to 20 hours, preferably 1 to 4 hours.
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 |
|---|---|
| CA2692533A1 true CA2692533A1 (en) | 2009-01-15 |
| CA2692533C CA2692533C (en) | 2013-03-05 |
Family
ID=38863117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2692533A Expired - Fee Related CA2692533C (en) | 2007-07-11 | 2008-06-16 | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US8637721B2 (en) |
| EP (1) | EP2167231B8 (en) |
| JP (1) | JP5158726B2 (en) |
| KR (1) | KR101241656B1 (en) |
| CN (1) | CN101720253B (en) |
| BR (1) | BRPI0813779B1 (en) |
| CA (1) | CA2692533C (en) |
| ES (1) | ES2394866T3 (en) |
| MY (1) | MY148675A (en) |
| RU (1) | RU2456078C2 (en) |
| SG (1) | SG183005A1 (en) |
| TW (1) | TWI415683B (en) |
| WO (1) | WO2009006979A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479382A (en) * | 2019-08-19 | 2019-11-22 | 迈瑞尔实验设备（上海）有限公司 | A kind of catalyst system and the preparation method and application thereof for ethylene selectivity oligomerisation 1- octene |
Families Citing this family (68)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2703021C (en) * | 2007-11-28 | 2015-01-20 | Vugar Aliyev | Catalyst composition and process for oligomerization of ethylene |
| ES2371218T3 (en) * | 2009-04-09 | 2011-12-28 | Saudi Basic Industries Corporation | COMPOSITION OF CATALYST AND PROCEDURE FOR THE OLIGOMERIZATION OF ETHYLENE. |
| CN102666443B (en) | 2009-10-16 | 2014-09-03 | 沙索技术有限公司 | 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 |
| CN102451759B (en) * | 2010-10-22 | 2015-09-09 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization, its Synthesis and applications |
| CN102451758B (en) * | 2010-10-22 | 2015-12-16 | 中国石油化工股份有限公司 | Catalyst for ethylene tetramerization, its Synthesis and applications |
| 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 |
| ES2409707T3 (en) | 2011-02-16 | 2013-06-27 | Linde Ag | Process for preparing a catalytic composition for oligomerization of ethylene and preforming unit of respective catalyst composition |
| CN103100420A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof |
| JP5844636B2 (en) * | 2011-12-27 | 2016-01-20 | 出光興産株式会社 | Method for producing α-olefin |
| KR101846031B1 (en) * | 2012-03-16 | 2018-04-05 | 에스케이이노베이션 주식회사 | Catalyst Systems for Preparing 1-Hexene and/or 1-Octene from Ethylene |
| BR112014027663A2 (en) | 2012-05-09 | 2017-06-27 | Sasol Tech Pty Ltd | process for the oligomerization of a hydrocarbon |
| KR102138685B1 (en) | 2012-05-09 | 2020-07-29 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | Tetramerisation of ethylene |
| CA2871215C (en) | 2012-05-09 | 2018-06-19 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream |
| MY164873A (en) | 2012-05-09 | 2018-01-30 | Sasol Tech Pty Ltd | Tetramerisation of ethylene |
| US9447202B2 (en) | 2012-05-09 | 2016-09-20 | Sasol Technology (Proprietary) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
| EP2684857A1 (en) * | 2012-07-10 | 2014-01-15 | Saudi Basic Industries Corporation | Method for oligomerization of ethylene |
| KR101483248B1 (en) | 2012-11-15 | 2015-01-16 | 주식회사 엘지화학 | Ligand compound, organic chromium compound, catalyst system for ethylene oligomerization, method for preparign the same, and method for ethylene oligomerization using the same |
| ES2524905T3 (en) * | 2012-11-28 | 2014-12-15 | Saudi Basic Industries Corporation | Process for the 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 |
| EP2764914A1 (en) | 2013-02-11 | 2014-08-13 | Linde AG | Metalated PNPNH ligand, catalyst composition and use thereof in the oligomerization of ethylene |
| EP2764913A1 (en) * | 2013-02-11 | 2014-08-13 | Linde AG | Method for purifying a crude PNPNH compound |
| KR101483247B1 (en) * | 2013-04-23 | 2015-01-16 | 주식회사 엘지화학 | Preparation method of catalyst for polyolefin polymerization and preparation method of polyolefin |
| KR102368171B1 (en) | 2013-05-09 | 2022-02-28 | 사솔 테크날러지 (프로프라이어터리) 리미티드 | Tetramerisation of ethylene |
| EP2994445B1 (en) * | 2013-05-09 | 2023-05-24 | Sasol Technology (Proprietary) Limited | Oligomerisation of ethylene to mixtures of 1-hexene and 1-octene |
| SG11201508461RA (en) | 2013-05-09 | 2015-11-27 | Sasol Tech Pty Ltd | 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 (en) | 2013-09-30 | 2016-07-12 | 주식회사 엘지화학 | Ligand compound, organic chromium compound, catalyst system for ethylene oligomerization and method for ethylene oligomerization using the same |
| CN104511311B (en) * | 2013-09-30 | 2017-07-07 | 华东理工大学 | A kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method |
| KR101601936B1 (en) | 2013-11-19 | 2016-03-09 | 주식회사 엘지화학 | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
| CA2933131A1 (en) * | 2014-01-06 | 2015-07-09 | Saudi Basic Industries Corporation | Modified preformation method for catalyst activation in ethylene reactions |
| KR20170035889A (en) * | 2014-07-24 | 2017-03-31 | 사빅 글로벌 테크놀러지스 비.브이. | Catalyst composition and process for oligomerization of ethylene to produce 1-hexene and/or 1-octene |
| KR101646178B1 (en) * | 2014-11-25 | 2016-08-05 | 롯데케미칼 주식회사 | Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
| KR101645611B1 (en) * | 2014-11-26 | 2016-08-05 | 롯데케미칼 주식회사 | Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
| KR101679515B1 (en) * | 2015-02-12 | 2016-11-24 | 주식회사 엘지화학 | Method of preparing catalyst system for oligomerization and catalyst sysyem for oligomerization prepared thereby |
| KR101768194B1 (en) | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | Catalyst composition and method for preparing polyolefin using the same |
| US10513474B2 (en) | 2015-05-15 | 2019-12-24 | Lg Chem, Ltd. | Catalyst composition and method of preparing polyolefin using the same |
| KR101757835B1 (en) | 2015-06-12 | 2017-07-13 | 주식회사 엘지화학 | Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins and method for oligomerization of olefins using the catalyst system |
| US10407359B2 (en) | 2015-09-16 | 2019-09-10 | Sabic Global Technologies B.V. | Process for deactivation of an olefin oligomerization catalyst |
| US10781147B2 (en) | 2015-12-22 | 2020-09-22 | Sabic Global Technologies B.V. | Methods for toluene recovery from linear alpha olefin production |
| KR101818180B1 (en) * | 2016-05-13 | 2018-02-21 | 한국화학연구원 | Method for oligomerization of ethylele |
| RU2749592C2 (en) * | 2016-12-30 | 2021-06-15 | Сабик Глобал Текнолоджис Б.В. | Method for obtaining a catalyst solution for the selective production of 1-hexene |
| WO2018122703A1 (en) | 2016-12-30 | 2018-07-05 | Sabic Global Technologies B.V. | Method for preparation of homogenous catalyst for selective 1-hexene production |
| US11117846B2 (en) | 2017-10-11 | 2021-09-14 | Lotte Chemical Corporation | Catalyst system for olefin oligomerization and method for preparing olefin oligomer by using same |
| CN109289928A (en) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | A kind of catalyst and preparation method thereof for ethylene oligomerization |
| WO2020100010A1 (en) * | 2018-11-12 | 2020-05-22 | Sabic Global Technologies B.V. | Ligands for production of 1-hexene in chromium assisted ethylene oligomerization process |
| CN111434670B (en) * | 2019-01-15 | 2021-07-30 | 中国石油化工股份有限公司 | Fluorine-containing compound and application thereof, ethylene oligomerization catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method |
| CA3126736A1 (en) | 2019-01-15 | 2020-07-23 | China Petroleum & Chemical Corporation | Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods |
| JP7402241B2 (en) * | 2019-01-15 | 2023-12-20 | 中国石油化工股▲ふん▼有限公司 | Halogen-containing compounds and uses, and ethylene oligomerization catalyst compositions and ethylene oligomerization methods, ethylene trimerization methods, and ethylene tetramerization methods |
| CN111434668B (en) * | 2019-01-15 | 2021-08-03 | 中国石油化工股份有限公司 | Halogen-containing compound, application thereof, catalyst composition, ethylene oligomerization method, ethylene trimerization method and ethylene tetramerization method |
| CN111889142B (en) * | 2020-07-23 | 2023-02-07 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN112473741B (en) * | 2020-10-22 | 2023-09-01 | 杭州小菱科技有限公司 | Ethylene oligomerization catalyst system and preparation method and application thereof |
| US11440857B2 (en) | 2020-11-30 | 2022-09-13 | Saudi Arabian Oil Company | Catalyst systems |
| US11612883B2 (en) | 2020-11-30 | 2023-03-28 | Saudi Arabian Oil Company | Catalyst systems |
| US11458462B2 (en) | 2020-11-30 | 2022-10-04 | Saudi Arabian Oil Company | Catalyst systems |
| US11623208B2 (en) | 2020-11-30 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems |
| WO2022115754A1 (en) | 2020-11-30 | 2022-06-02 | Saudi Arabian Oil Company | Catalyst systems |
| JP7280623B2 (en) * | 2020-12-28 | 2023-05-24 | 株式会社アビー | Cell cryopreservation solution and cell freezing method |
| 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 (en) * | 2021-12-01 | 2023-07-28 | 浙江智英石化技术有限公司 | Catalyst system containing pyrrole rigid structure multi-site ligand, preparation method and application |
| WO2023118226A1 (en) | 2021-12-23 | 2023-06-29 | Sabic Global Technologies B.V. | Catalyst composition for oligomerization reaction |
| US11623901B1 (en) | 2022-08-31 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems that include silyl ether moieties |
| US11639321B1 (en) | 2022-08-31 | 2023-05-02 | Saudi Arabian Oil Company | Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands |
| WO2024047612A1 (en) | 2022-09-02 | 2024-03-07 | Sabic Global Technologies B.V. | Methods for producing 1-hexene |
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 (en) * | 1996-04-04 | 2004-10-16 | Bp Chemicals Limited | A COMPOUND THAT CAN BE USED IN A CATALYTIC COMPOSITION. |
| 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 |
| CA2470885C (en) | 2001-12-20 | 2011-05-24 | 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 |
| WO2004056478A1 (en) * | 2002-12-20 | 2004-07-08 | Sasol Technology (Pty) Limited | Tetramerization of olefins |
| US7273959B2 (en) | 2003-10-10 | 2007-09-25 | Shell Oil Company | Catalytic trimerization of olefinic monomers |
| KR20080080570A (en) * | 2005-11-21 | 2008-09-04 | 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 | Catalytic process for the oligomerization of olefinic monomers |
| CN100386149C (en) * | 2006-06-26 | 2008-05-07 | 中国石油天然气股份有限公司 | Catalyst of ethylene trimerization, and application |
| DE102009027375A1 (en) | 2009-07-01 | 2011-03-10 | Robert Bosch Gmbh | Diagnostic method for making a diagnosis of a system |
-
2008
- 2008-06-16 BR BRPI0813779-0A patent/BRPI0813779B1/en not_active IP Right Cessation
- 2008-06-16 SG SG2012050308A patent/SG183005A1/en unknown
- 2008-06-16 JP JP2010515362A patent/JP5158726B2/en active Active
- 2008-06-16 ES ES08773451T patent/ES2394866T3/en active Active
- 2008-06-16 US US12/452,594 patent/US8637721B2/en active Active
- 2008-06-16 CA CA2692533A patent/CA2692533C/en not_active Expired - Fee Related
- 2008-06-16 KR KR1020107002616A patent/KR101241656B1/en active IP Right Grant
- 2008-06-16 MY MYPI20095649A patent/MY148675A/en unknown
- 2008-06-16 RU RU2010104668/04A patent/RU2456078C2/en active
- 2008-06-16 EP EP08773451A patent/EP2167231B8/en active Active
- 2008-06-16 CN CN2008800229456A patent/CN101720253B/en active Active
- 2008-06-16 WO PCT/EP2008/004815 patent/WO2009006979A2/en active Application Filing
- 2008-06-20 TW TW097123207A patent/TWI415683B/en not_active IP Right Cessation
-
2013
- 2013-12-20 US US14/135,674 patent/US9555404B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479382A (en) * | 2019-08-19 | 2019-11-22 | 迈瑞尔实验设备（上海）有限公司 | A kind of catalyst system and the preparation method and application thereof for ethylene selectivity oligomerisation 1- octene |
| CN110479382B (en) * | 2019-08-19 | 2022-04-29 | 迈瑞尔实验设备（上海）有限公司 | Catalyst system for preparing 1-octene through ethylene selective oligomerization, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2167231A2 (en) | 2010-03-31 |
| SG183005A1 (en) | 2012-08-30 |
| US9555404B2 (en) | 2017-01-31 |
| WO2009006979A2 (en) | 2009-01-15 |
| BRPI0813779A2 (en) | 2014-12-30 |
| RU2456078C2 (en) | 2012-07-20 |
| WO2009006979A3 (en) | 2009-03-26 |
| TWI415683B (en) | 2013-11-21 |
| CN101720253B (en) | 2013-07-17 |
| EP2167231B8 (en) | 2013-03-06 |
| JP5158726B2 (en) | 2013-03-06 |
| RU2010104668A (en) | 2011-08-20 |
| ES2394866T3 (en) | 2013-02-06 |
| TW200909055A (en) | 2009-03-01 |
| US8637721B2 (en) | 2014-01-28 |
| CN101720253A (en) | 2010-06-02 |
| KR20100046170A (en) | 2010-05-06 |
| JP2010532711A (en) | 2010-10-14 |
| BRPI0813779B1 (en) | 2018-06-26 |
| US20100190939A1 (en) | 2010-07-29 |
| US20140179970A1 (en) | 2014-06-26 |
| EP2167231B1 (en) | 2012-09-26 |
| MY148675A (en) | 2013-05-31 |
| CA2692533C (en) | 2013-03-05 |
| WO2009006979A8 (en) | 2009-12-23 |
| KR101241656B1 (en) | 2013-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2692533C (en) | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene | |
| CA2703021C (en) | Catalyst composition and process for oligomerization of ethylene | |
| US9018431B2 (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 | |
| CA2510190C (en) | Trimerisation of olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20210616 |