Olefins and methods for making the same

Patent metadata

Field	Value
Publication number	US-10294439-B2
Application number	US-201214112235-A
Country	US
Kind code	B2
Filing date	Feb 13, 2012
Priority date	Apr 13, 2011
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

Provided herein are olefinic feedstocks derived from conjugated hydrocarbon terpenes (e.g., C 10 -C 30 terpenes), methods for making the same, and methods for their use.

First claim

What is claimed is:

1. A method for making an olefinic feedstock comprising:
a) in a first stage, reacting C 15 -C 30 conjugated alkenes comprising at least one conjugated diene and at least one additional olefinic bond with hydrogen in the presence of a first catalyst under a first condition suitable to preferentially hydrogenate at least one olefinic bond in the at least one conjugated diene to produce partially hydrogenated intermediates, wherein the first condition comprises a type of first catalyst, a first catalyst loading, a reaction temperature, and a hydrogen pressure; and
b) in a second stage, reacting the partially hydrogenated intermediates with hydrogen in the presence of a second catalyst under a second condition to produce an olefinic feedstock comprising at least about 55% mono-olefins, wherein the second condition comprises a type of second catalyst, a second catalyst loading, a reaction temperature, and a hydrogen pressure;
wherein the type of catalyst, catalyst loading, reaction temperature, or hydrogen pressure is varied between the first stage and the second stage such that hydrogenation of partially hydrogenated intermediates having more than one olefinic bond is favored over hydrogenation of partially hydrogenated intermediates having one olefinic bond in the second stage; and
wherein in the second stage, the type of the second catalyst, the second catalyst loading, the reaction temperature, or the hydrogen pressure is controlled to produce the olefinic feedstock comprising at least about 55% mono-olefins.

2. The method of claim 1 , wherein the C 15 -C 30 conjugated alkenes are conjugated hydrocarbon terpenes.

3. The method of claim 1 , wherein the olefinic feedstock comprises at least about 60% mono-olefins.

4. The method of claim 1 , wherein the C 15 -C 30 conjugated alkenes are farnesenes.

5. The method of claim 4 , wherein the olefinic feedstock comprises at least about 70% hexahydrofarnesene and about 20% or less farnesane; or at least about 55% hexahydrofarnesene and about 5% or less tetrahydrofarnesene.

6. The method of claim 1 , wherein the first catalyst and/or the second catalyst comprises Pd, Pd/C, or Pd/Al 2 O 3 .

7. The method of claim 1 , wherein the temperature is raised between the first stage and the second stage, and/or the hydrogen pressure is reduced between the first stage and the second stage.

8. The method of claim 1 , wherein the olefinic feedstock comprises at least about 60% mono-olefins and less than about 25% alkanes.

9. The method of claim 8 , wherein the olefinic feedstock comprises about 10% or less di-olefins.

10. The method of claim 1 , wherein the olefinic feedstock comprises about 10% or less di-olefins.

11. The method of claim 10 , wherein the olefinic feedstock comprises about 5% or less di-olefins.

12. The method of claim 2 , wherein the conjugated hydrocarbon terpenes are conjugated C 15 terpenes, conjugated C 20 terpenes, conjugated C 25 terpenes, or conjugated C 30 terpenes.

13. The method of claim 1 , wherein in the first stage, the conditions are selected such that 5% or less of the partially hydrogenated intermediates contain conjugated carbon-carbon double bonds.

14. A method for making a mono-olefin terpene feedstock comprising:
a) in a first stage, reacting a conjugated terpene comprising at least one conjugated diene and at least one olefinic bond in addition to the at least one conjugated diene with hydrogen in the presence of a first catalyst under a first condition suitable to preferentially hydrogenate at least one olefinic bond in the at least one conjugated diene to produce a partially hydrogenated intermediate, wherein the first condition comprises a type of first catalyst, a first catalyst loading, a reaction temperature, and a hydrogen pressure; and
b) in a second stage, reacting the partially hydrogenated intermediate with hydrogen in the presence of a second catalyst under a second condition to produce a mono-olefin terpene feedstock comprising at least about 60% mono-olefins and less than about 25% alkanes, wherein the second condition comprises a type of second catalyst, a second catalyst loading, a reaction temperature, and a hydrogen pressure; and
wherein at least one of the type of catalyst, catalyst loading, reaction temperature, and hydrogen pressure is varied between the first stage and the second stage such that all but one of the olefinic double bonds of the partially hydrogenated intermediate are hydrogenated in the second stage;
wherein in the second stage, the type of the second catalyst, the second catalyst loading, the reaction temperature, or the hydrogen pressure is controlled to produce the mono-olefin terpene feedstock comprising at least about 60% mono-olefins and less than about 25% alkanes; and
wherein the conjugated terpene is selected from the group consisting of a conjugated C 15 terpene, a conjugated C 20 terpene, and a conjugated C 30 terpene.

15. The method of claim 14 , wherein the mono-olefin terpene feedstock comprises about 10% or less di-olefins.

16. The method of claim 14 , wherein the conjugated terpene is a conjugated C 15 terpene.

17. The method of claim 14 , wherein the mono-olefin feedstock comprises less than about 5% conjugated terpenes.

18. The method of claim 14 , wherein the mono-olefin terpene feedstock comprises at least about 70% mono-olefins and less than about 20% alkanes; at least about 75% mono-olefins and less than about 12% alkanes; at least about 80% mono-olefins and less than about 10% alkanes; or at least about 70% mono-olefins and about 5% or less di-olefins.

19. The method of claim 14 , wherein the conjugated terpene is β-farnesene or α-farnesene.

20. The method of claim 14 , wherein the first catalyst and/or the second catalyst comprises Pd, Pd/C, or Pd/Al 2 O 3 .

21. The method of claim 14 , wherein the conjugated terpene is produced by a bioengineered microorganism using a renewable carbon source.

22. A method for making a mono-olefin terpene feedstock comprising:
a) in a first stage, reacting a conjugated terpene comprising at least one conjugated diene and at least one olefinic bond in addition to the at least one conjugated diene with hydrogen in the presence of a first catalyst under a first condition suitable to preferentially hydrogenate at least one olefinic bond in the at least one conjugated diene to produce a partially hydrogenated intermediate, wherein the first condition comprises a type of first catalyst, a first catalyst loading, a reaction temperature, and a hydrogen pressure; and
b) in a second stage, reacting the partially hydrogenated intermediate with hydrogen in the presence of a second catalyst under a second condition to produce a mono-olefin terpene feedstock comprising at least about 55% mono-olefins and less than about 10% di-olefins, wherein the second condition comprises a type of second catalyst, a second catalyst loading, a reaction temperature, and a hydrogen pressure; and
wherein at least one of the type of catalyst, catalyst loading, reaction temperature, and hydrogen pressure is varied between the first stage and the second stage such that all but one of the olefinic double bonds of the partially hydrogenated intermediate are hydrogenated in the second stage;
wherein in the second stage, the type of the second catalyst, the second catalyst loading, the reaction temperature, or the hydrogen pressure is controlled to produce the mono-olefin terpene feedstock comprising at least about 55% mono-ole

Assignees

• Ohler Nicholas
• Fisher Karl
• Hong Jin Ki
• Amyris Inc

Inventors

• Ohler Nicholas
• Fisher Karl
• Hong Jin Ki

Classifications

• C10M2205/083

  used as base material · CPC title

• C10M2203/024

  unsaturated · CPC title

• C10M2203/022

  saturated · CPC title

• C10M2203/0206

  used as base material · CPC title

• C10M107/14

  containing conjugated diene · CPC title