Methods for treating substrates prior to metathesis reactions, and methods for metathesizing substrates
View Patent ↗A method for treating a substrate prior to a metathesis reaction includes treating the substrate with a first agent configured to mitigate potentially adverse effects of one or more contaminants in the substrate on a catalyst used to catalyze the metathesis reaction. The treating reduces a level of the one or more contaminants by an amount sufficient to enable the metathesis reaction to proceed at a substrate-to-catalyst molar ratio of at least about 7,500 to 1. Methods for metathesizing substrates are described.
1. A method of chemically treating a metathesis substrate, comprising:
providing a composition comprising a metathesis substrate and one or more catalyst poisoning contaminants, wherein the metathesis substrate is a natural oil; and
treating the composition to reduce the concentration of at least one of the one or more catalyst poisoning contaminants in the composition;
wherein the treating comprises contacting the composition with a metal alkyl compound.
2. The method of claim 1 , wherein the natural oil comprises a vegetable oil, an algae oil, a fish oil, an animal fat, a tall oil, any derivatives of the foregoing, or any combinations thereof.
3. The method of claim 1 , wherein the vegetable oil comprises 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, mustard oil, pennycress oil, camelina oil, castor oil, or combinations thereof.
4. The method of claim 1 , wherein the metathesis substrate comprises a fatty acid monoacylglyceride, a fatty acid diacylglyceride, a fatty acid triacylglyceriode, or a combination thereof.
5. The method of claim 1 , wherein the metathesis substrate comprises a fatty acid methyl ester.
6. The method of claim 1 , wherein the catalyst poisoning contaminants comprise water, peroxides, peroxide decomposition products, hydroperoxides, protic materials, polar materials, Lewis base catalyst poisons, or combinations thereof.
7. The method of claim 1 , wherein the catalyst poisoning contaminants comprise peroxides.
8. The method of claim 1 , wherein the catalyst poisoning contaminants comprise oxygenates.
9. The method of claim 1 , wherein the catalyst poisoning contaminants comprise compounds selected from the group consisting of alcohols, aldehydes, ethers, and combinations thereof.
10. The method of claim 1 , wherein the catalyst poisoning contaminants comprise aldehydes.
11. The method of claim 1 , wherein the metal alkyl compound is selected from the group consisting of: Group I metal alkyl compounds, Group II metal alkyl compounds, Group IIIA metal alkyl compounds, and any combinations thereof.
12. The method of claim 1 , wherein the metal alkyl compound is a compound of formula:
MR m ,
wherein:
M is a Group II metal or a Group IIIA metal;
each R is independently an alkyl group having 1 to 20 carbon atoms; and
m is 2 if M is a Group II metal, and is 3 if M is a Group IIIA metal.
13. The method of claim 12 , wherein M is magnesium, calcium, aluminum, or gallium.
14. The method of claim 12 , wherein M is aluminum.
15. The method of claim 12 , wherein each R is independently methyl, ethyl, butyl, hexyl, decyl, tetradecyl, or eicosyl.
16. The method of claim 1 , wherein the metal alkyl compound is selected from the group consisting of: Mg(CH 3 ) 2 , Mg(C 2 H 3 ) 2 , Mg(C 2 H 5 )(C 4 H 9 ), Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 12 H 25 ) 2 , Zn(CH 3 ) 2 , Zn(C 2 H 5 ) 2 , Zn(C 4 H 9 ) 2 , Zn(C 4 H 9 )(C 8 H 17 ), Zn(C 6 H 13 ) 2 , Zn(C 6 H 13 ) 2 , Al(C 2 H 5 ) 3 , Al(CH 3 ) 3 , Al(n−C 4 H 9 ) 3 , Al(C 8 H 17 ) 3 , Al(iso-C 4 H 9 ) 3 , Al(C 12 H 25 ) 3 , and combinations thereof.
17. The method of claim 16 , wherein metal alkyl compound is selected from the group consisting of: Al(C 2 H 5 ) 3 , Al(C 8 H 17 ) 3 , and combinations thereof.
18. The method of claim 1 , wherein the metal alkyl compound is a metal alkyl compound comprising one or more halogen or hydride groups.
19. The method of claim 18 , wherein the metal alkyl compound is ethylaluminum dichloride, diethylaluminum chloride, diethylaluminum hydride, Grignard reagents, diisobutylaluminum hydride, or combinations thereof.
20. The method of claim 1 , wherein the metal alkyl compound is a trialkyl aluminum compound, and wherein the treating comprises contacting the metathesis substrate with one or more of the materials selected from the group consisting of: a molecular sieve, alumina, silica gel, montmorillonite clay, fuller's earth, bleaching clay, diatomaceous earth, a zeolite, kaolin, an activated metal, an acid anhydride, activated carbon, doda ash, a metal anhydride, a metal sulfate, a metal halide, a metal carbonate, a metal silicate, phosphorus pentoxide, a metal aluminum halide, an alkyl aluminum hydride, a metal borohydride, an organometallic reagent, and a palladium on carbon catalyst.
21. The method of claim 1 , wherein the treating comprises heating the metathesis substrate to a temperature between 100° C. and 250° C.
22. The method of claim 1 , wherein the treating comprises contacting the metathesis substrate with an acid anhydride.
23. The method of claim 1 , wherein the treating comprises contacting the metathesis substrate with a desiccant.
24. The method of claim 1 , wherein the treating comprises contacting the metathesis substrate with an adsorbent.
25. A method of metathesizing a substrate, comprising:
treating a metathesis substrate according to the method of claim 1 ; and
metathesizing the treated substrate in the presence of a metathesis catalyst to form a metathesized product.