Methods of refining natural oil feedstocks

• US 8,957,268 B2
• Filed: 10/11/2010
• Issued: 02/17/2015
• Est. Priority Date: 10/12/2009
• Status: Active Grant

• Current Assignee: Wilmar Trading Pte., Ltd. (Wilmar International Limited)
• Original Assignee: Elevance Renewable Sciences Incorporated
• Inventors: Cohen, Steven A., Luetkens, Melvin L. Jr., Balakrishnan, Chander, Snyder, Robert
• Primary Examiner(s): Dang, Thuan D
• Application Number:
  US12/901,829
• Publication Number:
  US 20110113679A1
• Time in Patent Office: 1,590 Days
• Field of Search: 554/170, 585/14, 585/240, 585/250, 585/310, 585/324, 585/638, 585/639, 585/640
• US Class Current: 585/310
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2/862 the non-hydrocarbon contains only oxygen as hetero-atoms
• CPC Class Codes: C07C 2531/14 of aluminium or boron
• CPC Class Codes: C07C 2531/24 Phosphines
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 57/03 Monocarboxylic acids
• CPC Class Codes: C07C 57/12 Straight chain carboxylic acids containing eighteen carbon atoms
• CPC Class Codes: C07C 6/04 at a carbon-to-carbon double bond
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/54 by distillation
• CPC Class Codes: C07C 69/533 Monocarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/1018 of animal origin
• CPC Class Codes: C10G 2300/1092 C2-C4 olefins
• CPC Class Codes: C10G 2300/1096 Aromatics or polyaromatics
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/30 Physical properties of feedstocks or products
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2300/307 Cetane number, cetane index
• CPC Class Codes: C10G 2300/308 : Gravity, density, e.g. API
• CPC Class Codes: C10G 2300/44 : Solvents
• CPC Class Codes: C10G 2400/00 : Products obtained by processes covered by groups C10G9/00 - C10G69/14
• CPC Class Codes: C10G 2400/02 : Gasoline
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10G 2400/08 : Jet fuel
• CPC Class Codes: C10G 2400/20 : C2-C4 olefins
• CPC Class Codes: C10G 2400/22 : Higher olefins
• CPC Class Codes: C10G 3/42 : Catalytic treatment
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/58 : to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00
• CPC Class Codes: C10G 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10G 65/043 : at least one step being a change in the structural skeleton
• CPC Class Codes: C10G 69/02 : plural serial stages only
• CPC Class Codes: C10L 1/026 : for compression ignition
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 1/08 : for compression ignition
• CPC Class Codes: C10L 2200/0469 : Renewables or materials of biological origin
• CPC Class Codes: C11B 3/00 : Refining fats or fatty oils
• CPC Class Codes: C11C 1/08 : Refining
• CPC Class Codes: C11C 3/003 : by esterification of fatty acids with alcohols C11C3/02 takes precedence
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock
• CPC Class Codes: Y02T 50/678 : Aviation using fuels of non-fossil origin

Abstract

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.

Claims

1. A method of refining a natural oil, comprising:

providing (a) a feedstock comprising natural oil glycerides and (b) low-molecular-weight alpha-olefins;

cross-metathesizing the natural oil glycerides with the low-molecular-weight alpha-olefins in a metathesis reactor in the presence of a metathesis catalyst to provide a metathesized product comprising alpha-olefins and metathesized glycerides;

separating at least a portion of the alpha-olefins of the metathesized product and at least a portion of the metathesized glycerides of the metathesized product, to provide a first stream comprising separated alpha-olefins and second stream comprising separated metathesized glycerides;

transesterifying the separated metathesized glycerides of the second stream in the presence of an alcohol to provide a transesterified product comprising glycerin and fatty acid esters having no glycerin backbone; and

recycling at least a portion of the separated alpha-olefins of the first stream to the metathesis reactor.

2. The method of claim 1, further comprising treating the feedstock, prior to cross-metathesizing the natural oil glycerides with the low-molecular-weight alpha-olefins, under conditions sufficient to diminish catalyst poisons in the feedstock.

3. The method of claim 2, wherein the treating comprises chemically treating the feedstock through a chemical reaction with a reducing agent or a cation-inorganic base composition to diminish the catalyst poisons, wherein the reducing agent is selected from the group consisting of bisulfites, borohydrides, phosphines, thiosulfates, and phosphates.

4. The method of claim 2, wherein the treating comprises heating the feedstock to a temperature greater than 150°

C. in the absence of oxygen for a time sufficient to diminish the catalyst poisons.

5. The method of claim 1, further comprising separating the metathesis catalyst from the alpha-olefins and the metathesized glycerides 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 oligomerizing the separated alpha-olefins of the first stream to provide at least one of:

poly-alpha-olefins, poly-internal-olefins, mineral oil replacements, or biodiesel.

9. The method of claim 1, further comprising:

separating the glycerin from the transesterified product through a liquid-liquid separation;

after separating the glycerin, washing the transesterified product; and

after the washing, drying the transesterified product.

10. The method of claim 1, further comprising distilling the transesterified product to separate a specialty chemical, wherein the specialty chemical is a 9-decenoic acid ester, a 9-dodecenoic acid ester, or any combinations thereof.

11. The method of claim 10, further comprising hydrolyzing the specialty chemical to provide 9-decenoic acid, 9-dodecenonic acid, or any combinations thereof.

12. The method of claim 1, further comprising reacting the fatty acid esters of the transesterified product with themselves to provide a dibasic ester.

13. The method of claim 1, wherein the low-molecular-weight alpha-olefins comprise ethylene, propylene, 1-butene, or any combinations thereof.

14. The method of claim 1, further comprising hydrolyzing the fatty acid esters, thereby providing fatty acids.

15. The method of claim 1, wherein the natural oil glycerides comprise a natural oil triglyceride selected from the group consisting of vegetable oils, algae oils, animal fats, and combinations thereof.

16. The method of claim 1, wherein the natural oil glycerides comprise a vegetable oil selected from the group consisting of:

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, and combinations thereof.

17. The method of claim 1, wherein the natural oil glycerides comprise a vegetable oil selected from the group consisting of:

soybean oil, palm oil, canola oil, and combinations thereof.

18. The method of claim 1, wherein the alcohol is methanol or ethanol.

19. The method of claim 1, wherein the low-molecular-weight alpha-olefins comprise ethylene.

20. The method of claim 1, wherein the low-molecular-weight alpha-olefins comprise 1-butene.

21. The method of claim 1, wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises C2-C6 recycle alpha-olefins.

22. The method of claim 1, wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises C3-C5 recycle alpha-olefins.

23. The method of claim 1, wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises C3-C8 recycle alpha-olefins.

24. The method of claim 8, wherein the oligomerizing provides an olefin byproduct composition, and wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises the olefin byproduct composition.

25. The method of claim 1, further comprising partially hydrogenating the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor.

26. A method of refining a natural oil comprising:

providing (a) a feedstock comprising natural oil glycerides and (b) low-molecular-weight alpha-olefins having 4 to 10 carbon atoms;

cross-metathesizing the natural oil glycerides with the low-molecular-weight alpha-olefins in a metathesis reactor in the presence of a metathesis catalyst to provide a metathesized product comprising alpha-olefins and metathesized glycerides;

separating at least a portion of the alpha-olefins of the metathesized product and at least a portion of the metathesized glycerides of the metathesized product, to provide a first stream comprising separated alpha-olefins and a second stream comprising separated metathesized glycerides;

transesterifying the separated metathesized glycerides of the second stream in the presence of an alcohol to provide a transesterified product comprising glycerin and fatty acid esters having no glycerin backbone; and

recycling at least a portion of the separated alpha-olefins of the first stream to the metathesis reactor, wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises C2-C6 recycle alpha-olefins.

27. A method of refining a natural oil comprising:

providing (a) a feedstock comprising natural oil glycerides and (b) low-molecular-weight alpha-olefins comprising ethylene;

cross-metathesizing the natural oil glycerides with the low-molecular-weight alpha-olefins in a metathesis reactor in the presence of a metathesis catalyst to provide a metathesized product comprising alpha-olefins and metathesized glycerides;

separating at least a portion of the alpha-olefins of the metathesized product and at least a portion of the metathesized glycerides of the metathesized product, to provide a first stream comprising separated alpha-olefins and a second stream comprising separated metathesized glycerides;

transesterifying the separated metathesized glycerides of the second stream in the presence of an alcohol to provide a transesterified product comprising glycerin and fatty acid esters having no glycerin backbone; and

recycling at least a portion of the separated alpha-olefins of the first stream to the metathesis reactor, wherein the portion of the separated alpha-olefins of the first stream recycled to the metathesis reactor comprises C2-C6 recycle alpha-olefins.