Ethylene oligomerization processes

Patent metadata

Field	Value
Publication number	US-10793489-B2
Application number	US-201916696357-A
Country	US
Kind code	B2
Filing date	Nov 26, 2019
Priority date	Dec 22, 2017
Publication date	Oct 6, 2020
Grant date	Oct 6, 2020

Abstract

Disclosed herein is a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt; (iii) a second metal salt wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5:1 and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; (iv) an organoaluminum compound; and (b) forming an oligomer product. Also disclosed herein is a process comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand; (iii) a metal salt where an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5:1; (iv) an organoaluminum compound; and (b) forming an oligomer product.

First claim

We claim:

1. A process for forming an oligomer product comprising:
a) introducing into a reaction zone
i. ethylene;
ii. a heteroatomic ligand;
iii. a metal salt where
1) the metal salt is an iron salt, a cobalt salt, or any combination thereof, and
2) an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5:1;

iv. an organoaluminum compound wherein the organo groups of the organoaluminum compound are substantially devoid of β,γ-branched organo groups and β,δ-branched organo groups;
v. optionally hydrogen; and
vi. optionally an organic reaction medium; and

b) forming an oligomer product in the reaction zone;
wherein the oligomer product contains at least 70 weight percent products containing from 2 to 30 ethylene units.

2. The process of claim 1 , wherein a C 4 -C 20 productivity is at least 100% greater than the C 4 -C 20 productivity of an otherwise similar process wherein an equivalent molar ratio of the metal salt to the heteroatomic ligand is less than 1.1:1.

3. The process of claim 1 , wherein the heteroatomic ligand comprises 1) a bidentate metal salt complexing moiety or 2) a tridentate metal salt complexing moiety, wherein the bidentate metal salt complexing moiety and the tridentate metal salt complexing moiety each independently comprise at least two metal salt complexing groups selected from the group consisting of an imine group and an aromatic nitrogen atom containing group.

4. The process of claim 1 , wherein the organoaluminum compound comprises an aluminoxane.

5. The process of claim 4 , wherein the aluminoxane comprises methylaluminoxane, a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

6. The process of claim 1 , where the metal salt comprises an iron halide, an iron β-diketonate, an iron carboxylate, or any combination thereof.

7. The process of claim 1 , wherein the oligomer product is formed under conditions of i) an heteroatomic ligand molar equivalent concentration of at least 1×10 6 mmol/kg based upon the total kg mass of all components in the reaction zone, ii) an aluminum of the organo aluminum compound to heteroatomic ligand molar equivalent ratio of at least 100:1, iii) an aluminum of the organoaluminum compound concentration of at least 0.3 mmol Al/kg based upon the total kg mass of all components in the reaction zone, and iv) an ethylene partial pressure of at least 100 psi, a temperature of at least 0° C.

8. The process of claim 7 , wherein the equivalent molar ratio of the metal salt to the heteroatomic ligand ranges from 1.5:1 to 50:1 and the aluminoxane comprises methylaluminoxane, a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

9. The process of claim 1 , wherein the heteroatomic ligand and the metal salt are introduced to the reaction zone as separate and distinct components.

10. The process of claim 1 , wherein the heteroatomic ligand is a pyridine bisimine.

11. The process of claim 10 , wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine wherein the substituted aryl groups can be the same or different, or iii) an [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.

12. The process of claim 10 , wherein the pyridine bisimine has 1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group, none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group, and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 3) two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group, none, or one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group, and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 4) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group(s) and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 5) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are a quaternary carbon atom group and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, or 6) all four of the substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are fluorine.

13. The process of claim 10 , wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]pyridine, 2,6-bis[(2-ethylphenylimine)methyl]pyridine, 2,6-bis[(2-isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)-methyl]pyridine, 2,6-bis[(2,6-diethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.

14. The process of claim 10 , where the metal salt comprises an iron halide, an iron β-diketonate, an iron carboxylate, or any combination thereof.

15. The process of claim 14 , wherein the organoaluminum compound comprises an aluminoxane.

16. The process of claim 15 , wherein the aluminoxane comprises methylaluminoxane, a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

17. The process of claim 13 , where the metal salt comprises an iron halide, an iron β-diketonate, an iron carboxylate, or any combination thereof.

18. The process of claim 17 , wherein the oligomer product is formed under conditions of i) an heteroatomic ligand molar equivalent concentration of at leas

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Small Brooke L
• Milner Matthew F

Classifications

• C07C2531/14

  of aluminium or boron · CPC title

• C07C2531/28

  of the platinum group metals, iron group metals or copper · CPC title

• C07C2531/22

  Organic complexes · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07C2/32 Primary

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