Methods of refining natural oil feedstocks
Methods are provided for refining natural oil feedstocks. The methods comprise reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters. In certain embodiments, the methods further comprise separating the olefins from the esters in the metathesized product. In certain embodiments, the methods further comprise hydrogenating the olefins under conditions sufficient to form a fuel composition. In certain embodiments, the methods further comprise transesterifying the esters in the presence of an alcohol to form a transesterified product.
1. A method of refining a natural oil, comprising:
providing a feedstock comprising a natural oil;
reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product comprising olefins and esters;
separating the olefins in the metathesized product from the esters in the metathesized product;
transesterifying the esters in the presence of an alcohol to form a transesterified product; and
distilling the transesterified product to separate at least one specialty chemical;
hydrolyzing the at least one specialty chemical, thereby forming at least one acid selected from the group consisting of: 9-decenoic acid, 9-undecenoic acid, 9-dodecenonic acid, individually or in combinations thereof.
2. The method of claim 1 , further comprising treating the feedstock, prior to reacting the feedstock in the presence of a metathesis catalyst, under conditions sufficient to diminish catalyst poisons in the feedstock.
3. The method of claim 2 , wherein the feedstock is chemically treated through a chemical reaction to diminish the catalyst poisons.
4. The method of claim 2 , wherein the feedstock is heated to a temperature greater than 100° C. in the absence of oxygen and held at the temperature for a time sufficient to diminish the catalyst poisons.
5. The method of claim 1 , further comprising separating the metathesis catalyst from the olefins and esters with a water soluble phosphine reagent.
6. The method of claim 1 , wherein the metathesis catalyst is dissolved in a solvent.
7. The method of claim 6 , wherein the solvent is toluene.
8. The method of claim 1 , further comprising hydrogenating the olefins to form a fuel composition, wherein the fuel composition comprises either; a jet fuel composition having carbon number distribution between 5 and 16 or a diesel fuel composition having a carbon number distribution between 8 and 25.
9. The method of claim 1 , further comprising oligomerizing the olefins to form at least one of: poly-alpha-olefins; poly-internal-olefins, mineral oil replacements, or biodiesel.
10. The method of claim 1 , further comprising:
separating glycerin from the transesterified product through a liquid-liquid separation;
after separating the glycerin, washing the transesterified product with water to further remove the glycerin; and
after the washing; drying the transesterified product to separate the water from the transesterified product.
11. The method of claim 1 , wherein the hydrolyzing step further yields alkali metal salts and alkaline earth metal salts, individually or in combinations thereof, of the at least one acid.
12. The method of claim 1 , further comprising reacting the transesterified product with itself to form a dimer.
13. The method of claim 1 , wherein the reacting step comprises a self-metathesis reaction between the feedstock and itself.
14. The method of claim 1 , further comprising providing a low-molecular-weight olefin, wherein the reacting step comprises a cross-metathesis reaction between the feedstock and the low-molecular-weight olefin.
15. The method of claim 14 , wherein the low-molecular-weight olefin comprises at least one low-molecular-weight olefin selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, individually or in combinations thereof.
16. The method of claim 14 , wherein the low-molecular-weight olefin is an alpha-olefin.
17. The method of claim 14 , wherein the low-molecular-weight olefin comprises at least one branched olefin having a carbon number between 4 and 10.
18. The method of claim 17 , further comprising hydrogenating the low-molecular-weight olefin to form a fuel composition.
19. The method of claim 18 , wherein the fuel composition is: (a) a kerosene-type jet fuel having a carbon number distribution between 8 and 16, a flash point between approximately 38° C. and approximately 66° C., an auto ignition temperature of approximately 210° C., and a freeze point between approximately −47° C. and approximately −40° C.; (b) a naphtha-type jet fuel having a carbon number distribution between 5 and 15, a flash point between approximately −23° C. and approximately 0° C., an auto ignition temperature of approximately 250° C.; and a freeze point of approximately −65° C.; or (c) a diesel fuel having a carbon number distribution between 8 and 25, a specific gravity of between approximately 0.82 and approximately 1.08 at about 15.6° C., a cetane number of greater than approximately 40; and a distillation range between approximately 180° C. and approximately 340° C.
20. The method of claim 18 , further comprising:
flash-separating a light end stream from the metathesized product prior to separating the olefins from the esters, the light end stream having a majority of hydrocarbons with carbon number between 2 and 4; or
separating a light end stream from the olefins prior to hydrogenating the olefins, the light end stream having a majority of hydrocarbons with carbon numbers between 3 and 8; or
separating a C 18+ heavy end stream from the olefins prior to hydrogenating the olefins, the heavy end stream having a majority of hydrocarbons with carbon numbers of at least 18; or
separating a C 18+ heavy end stream from the fuel composition, the heavy end stream having a majority of hydrocarbons with carbon numbers of at least 18.