Thermal methods for treating a metathesis feedstock

• US 8,692,006 B2
• Filed: 08/11/2008
• Issued: 04/08/2014
• Est. Priority Date: 08/09/2007
• Status: Active Grant

• Current Assignee: Wilmar Trading Pte., Ltd. (Wilmar International Limited)
• Original Assignee: Elevance Renewable Sciences Incorporated
• Inventors: Uptain, Kevin D., Tanger, Charles, Kaido, Hiroki
• Primary Examiner(s): Carr, Deborah D
• Application Number:
  US12/672,652
• Publication Number:
  US 20110313180A1
• Time in Patent Office: 2,066 Days
• Field of Search: 554/124
• US Class Current: 554/124
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/4006 Temperature
• CPC Class Codes: C10G 2300/708 Coking aspect, coke content and composition of deposits
• CPC Class Codes: C10G 3/47 containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Various methods are provided for metathesizing a feedstock. In one aspect, a method includes providing a feedstock comprising a natural oil, heating the feedstock to a temperature greater than 100° C. in the absence of oxygen, holding the feedstock at the temperature for a time sufficient to diminish catalyst poisons in the feedstock, and, following the heating and holding, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

Claims

1. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil;

heating the feedstock to a temperature greater than 100°

C. in the absence of oxygen;

holding the feedstock at the temperature for a time sufficient to diminish catalyst poisons in the feedstock; and

following the heating and holding, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

5. The method of claim 1, wherein the temperature is less than or equal to 300°

C.

6. The method of claim 1, wherein the temperature is between approximately 120°

C. and 250°

C.

7. The method of claim 1, wherein the temperature is between approximately 150°

C. and 210°

C.

9. The method of claim 1, wherein the metathesis reaction comprises a maximum theoretical conversion limit, and wherein the metathesis catalyst catalyzes the metathesis of at least 50% of the maximum theoretical conversion limit.

10. The method of claim 9, wherein the metathesis catalyst metathesizes at least 70% of the maximum theoretical conversion limit.

11. The method of claim 9, having a catalyst loading of approximately 5 ppm/db or less.

12. The method of claim 11, wherein the catalyst loading is approximately 2 ppm/db or less.

13. The method of claim 9, wherein the metathesis catalyst metathesizes at least 85% conversion of the maximum theoretical conversion limit.

14. The method of claim 1, wherein the feedstock comprises a starting peroxide value of approximately greater than 5 meq/kg and the heating decreases the starting peroxide value of the feedstock to approximately 1 meq/kg or less.

15. The method of claim 14, wherein the heating comprises decreasing the starting peroxide value of the feedstock to approximately 0.5 meq/kg or less.

16. The method of claim 1 comprising any two or more of the following:

the combining comprises a catalyst loading of approximately 5 ppm/db or less, or approximately 3 ppm/db or less, or approximately 2 ppm/db or less, or approximately 1 ppm/db or less;

the metathesis reaction comprises a maximum theoretical conversion limit and the metathesis catalyst catalyzes the metathesis of at least 50 wt %, at least 70%, or at least 85% of the maximum theoretical conversion limit;

the temperature is between 100°

C. and 300°

C., or between 100°

C. and 250°

C., or between 150°

C. and 210°

C., or about 200°

C.;

the feedstock comprises a starting peroxide value of greater than 5 meq/kg, or greater than 10 meq/kg;

the heating decreases the peroxide value of the feedstock to a value of approximately 1 meq/kg or less or approximately 0.5 meq/kg or less;

after the heating, the feedstock is cooled to a temperature below approximately 40°

C. prior to the combining of the metathesis catalyst with the feedstock;

combining an adsorbent material with the feedstock to diminish the catalyst poisons in the feedstock, wherein the adsorbent material is selected from the group consisting of silica gel, bleaching clay, activated carbon, charcoal, molecular sieves, zeolites, Fuller'"'"'s earth, neutral alumina, basic alumina, Celite, aluminum sulfate, calcium carbonate, Kaolin, magnesium sulfate, potassium chloride, potassium magnesium sulfate, magnesium silicate, potassium sulfate, soda ash, sodium carbonate, and sodium sulfate;

combining an adsorbent material in an amount between approximately 0.1 and 3.0 wt % or between approximately 0.2 and 2.0 wt %; and

the feedstock comprises one or more materials selected from the group consisting of algae oil, canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, castor oil, and natural oil derivatives of any one or more of these.

20. The method of claim 1, wherein the temperature is about 200°

C.

2. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil;

heating the feedstock to a temperature greater than 100°

C. in the absence of oxygen;

holding the feedstock at the temperature for a time sufficient to diminish catalyst poisons in the feedstock;

combining an adsorbent material with the feedstock to diminish catalyst poisons in the feedstock; and

following the heating, the holding, and the combining steps, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

3. The method of claim 2, wherein the adsorbent is combined in an amount between approximately 0.1 and 3.0 wt % of the feedstock.

4. The method of claim 3, wherein the adsorbent is combined in an amount between approximately 0.2 and 2.0 wt % of the feedstock.

8. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil;

heating the feedstock to a temperature greater than 100°

C. in the absence of oxygen;

holding the feedstock at the temperature for a time sufficient to diminish catalyst poisons in the feedstock;

cooling the feedstock below approximately 40°

C.

following the cooling, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

17. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil;

heating the feedstock to a temperature greater than 100°

C. in the absence of oxygen for a time sufficient to diminish non-peroxide poisons in the feedstock; and

following the heating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

18. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil or a natural oil derivative, wherein the feedstock has a starting peroxide value;

heating the feedstock to a temperature greater than 100°

C. in the absence of oxygen for a time sufficient to diminish the starting peroxide value of the feedstock by approximately 80% or more; and

following the heating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

19. The method of claim 18, wherein the heating diminishes the starting peroxide value of the feedstock by approximately 90% or more.