Catalyst systems

Patent metadata

Field	Value
Publication number	US-11612883-B2
Application number	US-202117537646-A
Country	US
Kind code	B2
Filing date	Nov 30, 2021
Priority date	Nov 30, 2020
Publication date	Mar 28, 2023
Grant date	Mar 28, 2023

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 quaternary salts.

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 ) 2 P—Z—P(R 1 ) 2

wherein:
each R 1 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 2 )—, —P(R 2 )—, —B(R 2 )—, or —Si(R 2 ) 2 — that links the two P atoms, where R 2 is a (C 1 -C 50 ) alkyl group or a (C 6 -C 50 ) aryl group; and

an aluminum containing agent comprising a reaction product of an organoaluminum compound and an antifouling compound, wherein the antifouling compound comprises one or more quaternary salts.

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 quaternary salts have the structure:

wherein:
D is a nitrogen, phosphorus, arsenic, or sulfur;
A is an anion; and
R 6 , R 7 , R 8 , and R 9 are independently chosen from hydrogen, a (C 1 -C 50 ) hydrocarbyl group and a (C 1 -C 50 ) heterohydrocarbyl group.

5. 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.

6. 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 20 ) heterohydrocarbyl group.

7. The catalyst system of claim 1 , wherein the organoaluminum compound comprises one or more of triethylaluminum, tripropylaluminum, tri-iso-butylaluminum, diisobutylaluminium hydride, and trihexylaluminum.

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

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

10. The method of claim 9 , wherein the 1-octene is formed in condidions of: a reactor pressure from 5 bar to 120 bar; and a reactor temperature from 25° C. to 180° C.

Assignees

• Saudi Arabian Oil Co

Inventors

• Shaikh Sohel
• Khawaji Motaz
• Xu Wei

Classifications

• B01J31/1616 Primary

  Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00) · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J31/2409 Primary

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

• B01J2531/0297

  Non-coordinating anions · CPC title

• B01J31/143

  of aluminium · CPC title