METHODS AND APPARATUS FOR PRODUCING ALKYL ESTERS FROM LIPID FEED STOCKS AND SYSTEMS INCLUDING SAME

• US 20080051592A1
• Filed: 08/03/2007
• Published: 02/28/2008
• Est. Priority Date: 08/04/2006
• Status: Active Grant

• Current Assignee: Mcneff Research Consultants, Inc.
• Original Assignee: Sartec
• Inventors: Nowlan, Daniel, McNeff, Larry, Gyberg, Arlin, McNeff, Clayton, Yan, Bingwen
• Granted Patent: US 7,897,798 B2
• Time in Patent Office: Days
• US Class Current: 554/170
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C11C 3/003 by esterification of fatty acids with alcohols C11C3/02 takes precedence
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

The present invention relates to methods and apparatus for producing alkyl esters from lipid feed stocks, such as plant oils and/or animal fats, and systems including the same. In an embodiment, the invention includes a process for producing alkyl esters including mixing a lipid feed stock with an alcohol to form a reaction mixture; and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst comprising an unmodified metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia, and removing residual free fatty acids from the reaction mixture. Other embodiments are included herein.

Claims

1. A process for producing alkyl esters comprising:

mixing a lipid feed stock with an alcohol to form a reaction mixture;

contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst comprising an unmodified metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia, and removing residual free fatty acids from the reaction mixture.

2. The process of claim 1, the catalyst consisting essentially of an unmodified metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia.

3. The process of claim 1, the catalyst consisting essentially of titania.

4. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a temperature of between about 350 and 400 degrees Celsius.

5. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a pressure of between about 1500 and 5000 psi.

6. The process of claim 1, wherein contacting the reaction mixture with a catalyst is performed with a residence time of less than about 60 seconds.

7. The process of claim 1, wherein contacting the reaction mixture with a catalyst converts at least about 80% of triglycerides from the lipid feed stock into fatty acid alkyl esters as measured by NMR.

8. The process of claim 1, wherein removing residual free fatty acids from the reaction mixture comprises adding dimethyl carbonate to the reaction mixture.

9. The process of claim 1, wherein removing residual free fatty acids from the reaction mixture comprises adsorbing the free fatty acids to a metal oxide substrate and separating the reaction mixture from the metal oxide substrate.

10. The process of claim 1, the catalyst comprising particles with an average particle size of about 0.2 microns to about 2 millimeters.

11. The process of claim 1, wherein the catalyst has a porosity of between about 0.3 and 0.6.

12. The process of claim 1, wherein the catalyst has a pore volume of between about 0 and 0.6 mls/gram.

13. The process of claim 1, wherein the particulate metal oxide has a surface area of between about 1 and 200 m²/gram.

14. The process of claim 1, the alcohol comprising a C1-C6 alcohol.

15. The process of claim 1, further comprising adding a scent precursor compound comprising at least one carboxylic acid group to the reaction mixture before contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol.

16. The process of claim 1, the lipid feed stock including a component selected from the group consisting of acidulated soapstock, tall oil, rapeseed oil, soybean oil, canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, sunflower oil, poppy-seed oil, walnut oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm kernel oil, coconut oil, rice oil, algae oil, seaweed oil, Chinese Tallow tree oil, yellow grease, choice white grease, lard, tallow, brown grease, fish oil and poultry fat.

17. The process of claim 1, the lipid feed stock having an acid number of greater than or equal to about 3 mg KOH/g oil.

18. A process for producing alkyl esters comprising:

mixing a lipid feed stock with an alcohol to form a reaction mixture;

contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst comprising a metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia, wherein the metal oxide has been treated with a Bronsted acid or a Bronsted base, and

removing residual free fatty acids from the reaction mixture.

19. The process of claim 18, wherein the metal oxide has been treated with a Bronsted acid selected from the group consisting of hydrobromic acid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid, phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid, permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA).

20. The process of claim 18, wherein the metal oxide has been treated with sulfuric acid.

21. The process of claim 18, wherein the metal oxide has been treated with phosphoric acid.

22. The process of claim 18, wherein the metal oxide has been treated with a Bronsted base selected from the group consisting of consisting of sodium hydroxide and potassium hydroxide and lithium hydroxide.

23. A process for producing alkyl esters via transesterification or esterification from a feed stock comprising:

mixing the feed stock with an alcohol to form a reaction mixture, the feed stock comprising a triglyceride and/or a carboxylic acid; and

pumping the reaction mixture into a housing comprising a porous catalyst, the porous catalyst comprising an average particle size of about 0.2 microns to about 1 millimeter, the temperature and pressure within the housing comprising supercritical conditions for the alcohol, the porous catalyst comprising an unmodified metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia and

collecting a reaction product from the housing, the reaction product comprising esters in an amount at least equal to 80% of the triglyceride or carboxylic acid in the feed stock on a molar basis.