Catalyst systems

Patent metadata

Field	Value
Publication number	US-11458463-B2
Application number	US-202117537677-A
Country	US
Kind code	B2
Filing date	Nov 30, 2021
Priority date	Nov 30, 2020
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst having a structure according to Formula (VI) or Formula (VII). In Formulas (VI) and (VII), X is a halogen, a (C2-C30) carboxylate, acetylacetonate, or a (C1-C30) hydrocarbyl; L1 is a neutral coordinating ligand; n is an integer from 0 to 6; Y is a (C6-C20)fluorine-substituted aryl, a (C6-C20)fluorine-substituted aryloxy, or a (C1-C20)fluorine-substituted alkoxy; and L∩L is a bidentate chelating ligand. The catalyst system may also include an aluminum containing agent which includes a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more polyether alcohols or one or more non-polymeric ethers.

First claim

What is claimed is:

1. A catalyst system suitable for tetramerizing ethylene to form 1-octene, the catalyst system comprising:
a catalyst having the structure:
[(L∩L)CrX 2 (L 1 ) n ] + [BY 4 ] − or [(L∩L)CrX 2 (L 1 ) n ] + [SO 2 Y] −

wherein:
X is a halogen, a (C 2 -C 30 ) carboxylate, acetylacetonate, or a (C 1 -C 30 ) hydrocarbyl;
L 1 is a neutral coordinating ligand;
n is an integer from 0 to 6;
Y is a (C 6 -C 20 )fluorine-substituted aryl, a (C 6 -C 20 )fluorine-substituted aryloxy, or a (C 1 -C 20 )fluorine-substituted alkoxy; and
L∩L is a bidentate chelating ligand having the structure:
(R 1 )(R 2 )P—Z—P(R 1 )(R 2 )

wherein:
each R 1 and R 2 is independently chosen from a (C 1 -C 50 ) alkyl group or a (C 6 -C 50 ) aryl group; and
Z is a (C 2 -C 50 ) alkylene group, a (C 6 -C 50 ) arylene group, —N(R 7 )—,
—P(R 7 )—, —B(R 7 )—, or —Si(R 7 ) 2 — that links the two P atoms, where R 7 is a (C 1 -C 50 ) alkyl group or a (C 6 -C 50 ) aryl group; and

At least one aluminum containing agent comprising a reaction product of an organoaluminum compound and an antifouling compound, wherein the antifouling compound comprises one or more polyether alcohols or one or more non-polymeric ethers.

2. The catalyst system of claim 1 , wherein the catalyst has the structure:
[(L∩L)CrX 2 (L 1 ) n ] + [BY 4 ] − .

3. The catalyst system of claim 1 , wherein the catalyst has the structure:
[(L∩L)CrX 2 (L 1 ) n ] + [SO 2 Y] − .

4. The catalyst system of claim 1 , wherein the antifouling compound comprises one or more polyether alcohols.

5. The catalyst system of claim 1 , wherein the antifouling compound comprises one or more non-polymeric ethers.

6. The catalyst system of claim 1 , wherein each L 1 is a (C 2 -C 30 ) nitrile, a (C 2 -C 30 ) cyclic ether, a (C 2 -C 30 ) acyclic ether, or an H 2 O ligand.

7. The catalyst system of claim 1 , wherein the organoaluminum compound has the structure:

wherein R 3 , R 4 , and R 5 are each selected from a hydrogen atom, a (C 1 -C 20 ) hydrocarbyl group, and a (C 1 -C 50 ) heterohydrocarbyl group.

8. The catalyst system of claim 1 , wherein the organoaluminum compound comprises one or more of trimethylaluminium, triethylaluminum, tripropylaluminum, tri-iso-butylaluminum, diisobutylaluminium hydride, trihexylaluminum, tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminium isopropoxide, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, methylaluminoxane (MAO), ethylaluminoxane (EAO), and modified methylaluminoxane (MMAO).

9. The catalyst system of claim 1 , wherein the molar ratio of the antifouling compound to the organoaluminum compound is from 0.001 to 1.

10. A method for tetramerizing ethylene to form 1-octene, the method comprising contacting ethylene with the catalyst system of claim 1 to form a product comprising 1-octene.

11. The method of claim 10 , wherein the ethylene is formed in conditions of:
a reactor pressure from 5 bar to 120 bar; and
a reactor temperature from 25° C. to 180° C.

12. A method of making a catalyst system suitable for tetramerizing ethylene to form 1-octene, the method comprising mixing a chromium compound, an anion-containing compound, a bidentate chelating ligand, and an aluminum containing agent to form the catalyst system, wherein the aluminum containing agent is a reaction product of an organoaluminum compound and an antifouling compound, and wherein the antifouling compound comprises one or more polyether alcohols or one or more non-polymeric ethers.

13. The method of claim 12 , wherein the chromium compound has the structure:
CrX 3 (L 1 ) n
wherein:
X is a halogen, a (C 2 -C 30 ) carboxylate, acetylacetonate, or a (C 1 -C 30 ) hydrocarbyl;
L 1 is a ligand; and
n is an integer from 0 to 6.

14. The method of claim 12 , wherein the anion containing compound has a structure:
M + [BY 4 ] −
wherein:
Y is a (C 6 -C 20 )fluorine-substituted aryl, a (C 6 -C 20 )fluorine-substituted aryloxy, or a (C 1 -C 20 )fluorine-substituted alkoxy; and
M + is a metal inorganic cation or an organic cation.

15. The method of claim 12 , wherein the anion containing compound has a structure:
M + [SO 2 Y] −
wherein:
Y is a (C 6 -C 20 )fluorine-substituted aryl, a (C 6 -C 20 )fluorine-substituted aryloxy, or a (C 1 -C 20 )fluorine-substituted alkoxy; and
M + is a metal inorganic cation or an organic cation.

16. The method of claim 12 , wherein the bidentate chelating ligand has the structure:
(R 1 )(R 2 )P—Z—P(R 1 )(R 2 )

wherein:
each R 1 and R 2 is independently chosen from a (C 1 -C 50 ) alkyl group or a (C 6 -C 50 ) aryl group; and
Z is a (C 2 -C 50 ) alkylene group, a (C 6 -C 50 ) arylene group, —N(R 7 )—, —P(R 7 )—, —B(R 7 )—, or —Si(R 7 ) 2 — that links the two P atoms, where R 7 is a (C 1 -C 50 ) alkyl group or a (C 6 -C 50 ) aryl group.

Assignees

• Saudi Arabian Oil Co

Inventors

• Khawaji Motaz
• Shaikh Sohel
• Xu Wei

Classifications

• B01J31/2409 Primary

  with more than one complexing phosphine-P atom · CPC title

• B01J31/143

  of aluminium · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• C07C7/20

  Use of additives, e.g. for stabilisation · CPC title