Chemical methods for treating a metathesis feedstock

• US 8,642,824 B2
• Filed: 08/11/2008
• Issued: 02/04/2014
• 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: Lemke, Daniel W., Uptain, Kevin D., Amore, Francis, Abraham, Tim
• Primary Examiner(s): Cutliff, Yate K
• Application Number:
  US12/672,651
• Publication Number:
  US 20110160472A1
• Time in Patent Office: 2,003 Days
• Field of Search: None
• US Class Current: 585/500
• CPC Class Codes: C07C 6/04 at a carbon-to-carbon double bond
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• 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: C11B 3/02 by chemical reaction C11B3/003 takes precedence
• CPC Class Codes: C11B 3/04 with acids
• CPC Class Codes: C11B 3/06 with bases
• CPC Class Codes: C11B 3/10 by adsorption
• 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, chemically treating the feedstock under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, 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;

chemically treating the feedstock with a reducing agent under conditions sufficient to diminish catalyst poisons in the feedstock through a chemical reaction of the catalyst poisons producing a treated feedstock; and

following chemically treating, combining a metathesis catalyst with the treated feedstock under conditions sufficient to metathesize the treated feedstock in a metathesis reaction,

wherein the reducing agent is selected from the group consisting of bisulfites, phosphines, and thiosulfates.

2. The method of claim 1, wherein the reducing agent is added at a level of between about 0.1 wt % and about 0.9 wt % of the feedstock.

3. The method of claim 1, wherein the chemically treating is conducted at a temperature between approximately 25°

C. and 90°

C.

4. The method of claim 1 further comprising combining an adsorbent material with the feedstock or the treated feedstock.

5. The method of claim 4, comprising combining the adsorbent material in an amount between approximately 0.1 and 3.0 wt %.

6. The method of claim 5, comprising combining the adsorbent material in an amount between approximately 0.2 and 2.0 wt %.

7. 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.

8. The method of claim 7, wherein the metathesis catalyst catalyzes the metathesis of at least 70% of the maximum theoretical conversion limit.

9. The method of claim 8, having a catalyst loading of approximately 5 ppm/db or less.

10. The method of claim 9, wherein the catalyst loading is approximately 2 ppm/db or less.

11. The method of claim 7, wherein the metathesis catalyst catalyzes metathesis of at least 85% conversion of the maximum theoretical conversion limit.

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

13. The method of claim 12, wherein the chemically treating decreases the starting peroxide value of the feedstock to approximately 0.5 meq/kg or less.

14. 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 chemically treating comprises treating the feedstock under conditions sufficient to diminish non-peroxide poisons in the feedstock;

the chemically treating is conducted at a temperature between approximately 25°

C. and 90°

C., or between approximately 50°

C. and 80°

C.;

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

the chemically treating 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;

combining an adsorbent material to diminish the catalyst poisons within the feedstock or the treated 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 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.

15. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil;

chemically treating the feedstock with a reducing agent under conditions sufficient to diminish non-peroxide poisons in the feedstock through a chemical reaction of the non-peroxide poisons producing a treated feedstock; and

following chemically treating, combining a metathesis catalyst with the treated feedstock under conditions sufficient to metathesize the treated feedstock in a metathesis reaction,

wherein the reducing agent is selected from the group consisting of bisulfites, phosphines, and thiosulfates.

16. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil having a starting peroxide value;

chemically treating the feedstock with a reducing agent for a time sufficient to reduce the starting peroxide value of the feedstock by approximately 80% or more through a chemical reaction of the peroxide poisons producing a treated feedstock;

following chemically treating, combining a metathesis catalyst with the treated feedstock under conditions sufficient to metathesize the treated feedstock in a metathesis reaction,

wherein the reducing agent is selected from the group consisting of bisulfites, phosphines, and thiosulfates.

17. The method of claim 16, wherein the treating decreases the starting peroxide value of the feedstock by approximately 90% or more.

18. A method of metathesizing a feedstock comprising:

providing a feedstock comprising a natural oil having a peroxide value of greater than 5 meq/kg;

decreasing the peroxide value to 0.5 meq/kg or less by chemically treating the feedstock with a reducing agent or a cation-inorganic base composition producing a treated feedstock;

and then, combining a metathesis catalyst with the treated feedstock under conditions sufficient to metathesize the treated feedstock in a metathesis reaction, 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.

19. The method of claim 18, further comprising adding an adsorbent material to the feedstock or the treated feedstock.

20. The method of claim 18, having a catalyst loading of approximately 5 ppm/db or less.

21. The method of claim 20, wherein the metathesis catalyst catalyzes the metathesis of at least 70% of the maximum theoretical conversion limit.

22. The method of claim 18, having a catalyst loading of approximately is approximately 3 ppm/db or less.

23. The method of claim 22, wherein the metathesis catalyst catalyzes the metathesis of at least 70% of the maximum theoretical conversion limit.

24. The method of claim 22, wherein the metathesis catalyst catalyzes metathesis of at least 85% conversion of the maximum theoretical conversion limit.