Alkylation process using phosphonium-based ionic liquids

Patent metadata

Field	Value
Publication number	US-9399604-B2
Application number	US-201313796814-A
Country	US
Kind code	B2
Filing date	Mar 12, 2013
Priority date	Jun 26, 2012
Publication date	Jul 26, 2016
Grant date	Jul 26, 2016

Abstract

A process for making an alkylate is presented. The process includes mixing an isoparaffin stream with an olefin stream in an alkylation reactor. The alkylation reactor includes a catalyst for performing the reaction. The catalyst is an ionic liquid that is a quaternary chloroaluminate based ionic liquid, and the reaction is performed at or near ambient temperatures.

First claim

The invention claimed is:

1. A process for the alkylation of isoparaffins comprising:
passing an isoparaffin having from 4 to 10 carbon atoms to an alkylation reactor; and
passing an olefin having from 2 to 10 carbon atoms to the alkylation reactor, wherein the alkylation reactor is operated at reaction conditions and has an unsupported ionic liquid catalyst, comprising a haloaluminate with an aluminum halide (AlX 3 ) molar fraction of the haloaluminate is greater than 0.5 and wherein X is selected from the group consisting of Cl, Br, I and mixtures thereof, for reacting the olefin and the isoparaffin to generate an alkylate, wherein the ionic liquid catalyst has an initial kinematic viscosity of at least 50 cSt at a temperature of 20° C.;
wherein the ionic liquid catalyst has a structure of the form PR1R2R3R4-Al 2 X 7 , wherein P refers to the phosphonium cation part of the ionic liquid catalyst, X refers to a halogen atom, and R1, R2, R3 and R4 are alkyl groups having between 4 and 12 carbon atoms, and wherein the structure further includes that the R1, R2 and R3 alkyl groups are the same alkyl group, and the R4 alkyl group comprises a different alkyl group than the R1, R2 and R3 alkyl groups, and wherein the volume fraction of the ionic liquid catalyst is less than 30% of a reaction mixture, and wherein the reaction mixture refers to a mixture of the ionic liquid catalyst and hydrocarbons contained in the alkylation reactor.

2. The process of claim 1 , wherein the ionic liquid catalyst is a chloroaluminate ionic liquid having a kinematic viscosity of at least 20 cSt at 50° C.

3. The process of claim 1 , wherein the alkylate generated has an octane number of at least 90.

4. The process of claim 1 , wherein the reaction conditions include a reaction temperature greater than 0° C.

5. The process of claim 4 , wherein the reaction conditions include a reaction temperature greater than or equal to 20° C.

6. The process of claim 4 , wherein the reaction conditions include a reaction temperature greater than or equal to 20° C., and less than or equal to 70° C.

7. The process of claim 1 , wherein the isoparaffin has from 4 to 8 carbon atoms.

8. The process of claim 7 , wherein the isoparaffin has from 4 to 5 carbon atoms.

9. The process of claim 1 , wherein the olefin has from 3 to 8 carbon atoms.

10. The process of claim 9 , wherein the olefin has from 3 to 5 carbon atoms.

11. An alkylation process comprising:
passing an isoparaffin stream and an olefin stream to an alkylation reactor, wherein the isoparaffin stream comprises isoparaffins having from 4 to 8 carbon atoms and the olefin stream comprises olefins having from 3 to 10 carbon atoms;
reacting the isoparaffins and the olefins in the presence of an unsupported ionic liquid catalyst at reaction conditions to generate an alkylate, wherein the ionic liquid catalyst has an initial kinematic viscosity of at least 50 cSt at 20° C., wherein the ionic liquid catalyst comprises a haloaluminate and has aluminum halide (AlX 3 ) molar fraction of the haloaluminate is greater than 0.5 and wherein X is selected from the group consisting of Cl, Br, I and mixtures thereof;
wherein the ionic liquid catalyst has a structure of the form PR1R2R3R4-Al 2 X 7 , wherein P refers to the phosphonium cation part of the ionic liquid catalyst, X refers to a halogen atom, and R1, R2, R3 and R4 are alkyl groups having between 4 and 12 carbon atoms, and wherein the structure further includes that the R1, R2 and R3 alkyl groups are the same alkyl group, and the R4 alkyl group comprises a different alkyl group than the R1, R2 and R3 alkyl groups, and wherein the volume fraction of the ionic liquid catalyst is less than 30% of a reaction mixture, and wherein the reaction mixture refers to a mixture of the ionic liquid catalyst and hydrocarbons contained in the alkylation reactor.

12. The process of claim 11 , wherein the ionic liquid catalyst has a kinematic viscosity of at least 20 cSt at 50° C.

13. The process of claim 11 , wherein the alkylate generated has an octane number of at least 85.

14. The process of claim 11 , wherein the reaction conditions include a reaction temperature greater than 20° C.

15. The process of claim 11 , wherein the reaction conditions include a reaction temperature greater than or equal to 20° C., and less than or equal to 50° C.

16. The process of claim 11 , wherein the isoparaffin has from 4 to 5 carbon atoms.

17. The process of claim 11 , wherein the olefin has from 3 to 8 carbon atoms.

18. The process of claim 17 , wherein the olefin has from 3 to 5 carbon atoms.

19. The process of claim 11 , wherein the ionic liquid catalyst is selected from the group consisting of tributyl-hexylphosphonium-Al 2 X 7 , tributylpentylphosphonium-Al 2 X 7 , tributylheptylphosphonium-Al 2 X 7 , tributyloctylphosphonium-Al 2 X 7 , and mixtures thereof, wherein X comprises a halogen atom selected from the group consisting of Cl, Br, I and mixtures thereof.

20. A process for the alkylation of isoparaffins comprising:
passing an isoparaffin having from 4 to 10 carbon atoms to an alkylation reactor; and
passing an olefin having from 2 to 10 carbon atoms to the alkylation reactor, wherein the alkylation reactor is operated at reaction conditions and has an unsupported ionic liquid catalyst, comprising a haloaluminate with an aluminum halide (AlX 3 ) molar fraction of the haloaluminate is greater than 0.5 and wherein X is selected from the group consisting of Cl, Br, I and mixtures thereof, for reacting the olefin and the isoparaffin to generate an alkylate, wherein the ionic liquid catalyst has an initial kinematic viscosity of at least 50 cSt at a temperature of 20° C., and wherein the volume fraction of the ionic liquid catalyst is less than 30% of a reaction mixture, and wherein the reaction mixture refers to a mixture of the ionic liquid catalyst and hydrocarbons contained in the alkylation reactor,
wherein the ionic liquid catalyst has a structure of the form PR1R2R3R4-Al 2 X 7 , wherein P refers to the phosphonium cation part of the ionic liquid catalyst, X refers to a halogen atom, and R1, R2, and R3 are the same alkyl group having 4 carbon atoms, and the R4 alkyl group comprises a different alkyl group than the R1, R2 and R3 alkyl groups having 5 or 6 carbon atoms.

Assignees

• Uop Llc

Inventors

• Martins Susie C
• Nafis Douglas A
• Bhattacharyya Alakananda

Classifications

• C07C2/56 Primary

  Addition to acyclic hydrocarbons · CPC title

• C07C2/60 Primary

  with halides · CPC title

• C07C2531/02

  containing organic compounds or metal hydrides · CPC title

• C10G2300/1092

  C2-C4 olefins · CPC title

• B01J2231/44

  Allylic alkylation, amination, alkoxylation or analogues · CPC title