Catalyst systems

Patent metadata

Field	Value
Publication number	US-11623208-B2
Application number	US-202117537657-A
Country	US
Kind code	B2
Filing date	Nov 30, 2021
Priority date	Nov 30, 2020
Publication date	Apr 11, 2023
Grant date	Apr 11, 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 (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. 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 organic acids, organic acid salts, esters, anhydrides, or combinations of these.

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 8 )—, —P(R 8 )—, —B(R 8 )—, or —Si(R 8 ) 2 — that links the two P atoms, where R 8 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 organic acids, organic acid salts, esters, anhydrides, or combinations of these.

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 organic acids.

5. The catalyst system of claim 1 , wherein the antifouling compound comprises one or more organic acid salts.

6. The catalyst system of claim 1 , wherein the antifouling compound comprises one or more esters.

7. The catalyst system claim 1 , wherein the antifouling compound comprises one or more anhydrides.

8. 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.

9. 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).

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

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

• C07C2/36

  as phosphines, arsines, stilbines or bismuthines · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title