Process and catalyst composition for producing linear alpha olefins in high yield by ethylene oligomerization

Patent metadata

Field	Value
Publication number	US-12252576-B2
Application number	US-202218058377-A
Country	US
Kind code	B2
Filing date	Nov 23, 2022
Priority date	Nov 23, 2021
Publication date	Mar 18, 2025
Grant date	Mar 18, 2025

Abstract

The present disclosure relates to a process for producing linear alpha olefins in high yield carried out by oligomerization of ethylene in the presence of a novel catalyst composition. The catalyst composition includes Zirconium compound, an organoaluminum compound, and at least one Lewis base selected from cyclic and acyclic ethers (i.e., di-n-butyl ether and diethyl ether). The process for oligomerization of ethylene is carried out in an inert organic solvent in the presence of said catalyst composition. The process as disclosed herein provides significantly high activity of the said catalyst composition resulting in high yield of the alpha olefins (>95 wt. %) as the product and significantly minimum polymer as by-product. The process provides higher yield of C6-C10 fraction with >60 wt. %.

First claim

We claim:

1. A catalyst composition for producing linear alpha olefins by oligomerization of ethylene, the catalyst composition consisting of:
(i) a zirconium compound, wherein the zirconium compound is combination of tetrachlorobis (tetrahydrofuran) zirconium (ZrCl 4 ·2THF), ZrCl 4 ·2 (N,N-diisobutylacetamide) wherein ZrCl 4 ·2THF and ZrCl 4 ·2 (N,N-diisobutylacetamide) are in a mole ratio of 1:1;
(ii) an organoaluminum compound having a formula R 1 n AlY 3-n , or a formula Al 2 Y 3 R 1 3 , wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, Y represents Cl, Br, or I, n is a number 1≤n≤2; and
iii) at least one Lewis base, wherein the Lewis base is selected from a group consisting of cyclic and acyclic ethers.

2. The catalyst composition as claimed in claim 1 , wherein the organoaluminum compound is selected from the group consisting of diethylaluminum chloride, ethylaluminum sesquichloride and a mixture thereof.

3. The catalyst composition as claimed in claim 1 , wherein aluminum present in the organoaluminum compound and zirconium present in the zirconium compound are in a mole ratio in a range of 10:1 to 70:1.

4. The catalyst composition as claimed in claim 1 , wherein the cyclic and acyclic ethers are at least one of cycloaliphatic ethers, aromatic ethers, monoethers, diethers, tetraethers and polyethers.

5. The catalyst composition as claimed in claim 1 , wherein the cyclic and acyclic ethers are selected from the group consisting of diethyl ether, di-n-butyl ether, di-n-propyl ether, diisobutyl ether, diisopropyl ether, diphenyl ether, methyl butyl ether, methyl phenyl ether, dicyclohexyl ether, tert-butyl methyl ether, divinyl ether, 1,2 dimethoxy ethane, ethylene glycol dimethyl ether, and a mixture thereof.

6. The catalyst composition as claimed in claim 1 , wherein the zirconium in the zirconium compound and the Lewis base are in a mole ratio in a range of 1:10 to 1:30.

7. A process for preparing a catalyst composition to produce linear alpha olefins by oligomerization of ethylene, the process comprising:
mixing a zirconium compound, an organoaluminum compound, at least one Lewis base and an inert organic solvent in a reactor; and
forming the catalyst composition in situ in the reactor,
wherein the zirconium compound has a formula ZrX m ·nA, wherein X is a halogen atom, m is an integer having a value equal to or less than 4, n is a number equal to or less than 2, and A is selected from the group consisting of tetrahydrofuran, N,N-diisobutylacetamide and a combination thereof,
wherein the organoaluminum compound has a formula R 1 n AlY 3-n , or a formula Al 2 Y 3 R 1 3 , wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, Y represents Cl, Br or I, n is a number 1≤n≤2, and
wherein the Lewis base is selected from a group consisting of cyclic and acyclic ethers.

8. The process as claimed in claim 7 , wherein the inert organic solvent is selected from the group consisting of unsubstituted aromatic hydrocarbons, aromatic hydrocarbons substituted with halogens, aliphatic paraffin hydrocarbons, alicyclic hydrocarbon compounds, halogenated alkanes, and a mixture thereof.

9. A process for producing linear alpha olefins by oligomerization of ethylene in the presence of a catalyst composition, the process consisting of:
preparing a catalyst composition in a reactor at ambient temperature;
charging ethylene into an oligomerization reactor;
charging the catalyst composition into the oligomerization reactor under an inert atmosphere at a reaction temperature between 50° C. to 150° C.; and
producing about 95 wt. % of linear alpha olefins and traces of polymer by-product, wherein the catalyst composition consists of:
a combination of ZrCl 4 ·2THF and ZrCl 4 ·2 (N,N-diisobutylacetamide) wherein ZrCl 4 ·2THF and ZrCl 4 ·2 (N,N-diisobutylacetamide) are in a mole ratio of 1:1;
an organoaluminum compound having a formula R 1 n AlY 3-n , or a formula Al 2 Y 3 R 1 3 , wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, Y represents Cl, Br, or I, n is a number 1≤n≤2; and

at least one Lewis base, wherein the Lewis base is selected from a group consisting of cyclic and acyclic ethers.

10. The process as claimed in claim 9 , wherein the linear alpha olefins have a weight percent distribution of C4-C24 carbon.

11. The process as claimed in claim 9 , wherein the linear alpha olefins have greater than 60 wt. % of C6-C10 fraction.

12. The process as claimed in claim 9 , wherein the reaction temperature is between 60° C. to 110° C.

13. The process as claimed in claim 9 , wherein preparing the catalyst composition in the reactor at ambient temperature comprises:
mixing a zirconium compound, an organoaluminum compound, at least one Lewis base and an inert organic solvent in the reactor; and
forming the catalyst composition in situ in the reactor.

14. The process as claimed in claim 13 , wherein the inert organic solvent is selected from the group consisting of unsubstituted aromatic hydrocarbons, aromatic hydrocarbons substituted with halogens, aliphatic paraffin hydrocarbons, alicyclic hydrocarbon compounds, halogenated alkanes, and a mixture thereof.

15. The process as claimed in claim 14 , wherein the substituted aromatic hydrocarbons are selected from the group consisting of toluene, benzene, xylene, chlorobenzene, dichlorobenzene, and chlorotoluene.

16. The process as claimed in claim 14 , wherein the aliphatic paraffin hydrocarbons are selected from the group consisting of pentane, hexane, heptane, octane, nonane, and decane.

17. The process as claimed in claim 14 , wherein the alicyclic hydrocarbon compounds are cyclohexane, or decahydronaphthalene.

18. The process as claimed in claim 14 , wherein the halogenated alkanes are dichloroethane, or dichlorobutane.

19. The process as claimed in claim 9 , wherein the inert atmosphere is provided by nitrogen or argon.

Assignees

• Indian Oil Corp Ltd

Inventors

• Kaur Sukhdeep
• Rani Rashmi
• Singh Gurmeet
• Singh Dheer
• Chopra Anju
• Kapur Gurpreet Singh
• RAMAKUMAR Sankara Sri Venkata

Classifications

• B01J31/22

  Organic complexes · CPC title

• B01J31/14

  of aluminium or boron · CPC title

• C07C2/32

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

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C07C2531/14

  of aluminium or boron · CPC title