Single-phase process for production of fatty acid methyl esters from mixtures of triglycerides and fatty acids

• US 6,642,399 B2
• Filed: 07/22/2002
• Issued: 11/04/2003
• Est. Priority Date: 08/18/1999
• Status: Expired due to Term

• Current Assignee: BIOX Corporation (Clearwater Fine Foods, Inc.)
• Original Assignee: 1523808 Ontario Inc.
• Inventors: Boocock, David Gavin Brooke
• Primary Examiner(s): Carr, Deborah D.
• Application Number:
  US10/199,359
• Publication Number:
  US 20030083514A1
• Time in Patent Office: 470 Days
• Field of Search: 554/167, 554/164, 554/163, 554/170
• US Class Current: 554/167
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/24 esterified with monohydroxylic compounds
• CPC Class Codes: C07C 69/52 Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
• CPC Class Codes: C10L 1/026 for compression ignition
• 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

Abstract

A process for the esterification of a mixture of fatty acids and triglycerides. The process comprises forming a single phase solution of fatty acids and triglyceride in an alcohol selected from methanol and ethanol, the ratio of said alcohol to triglyceride being 15:1 to 35:1. The solution further comprises a co-solvent in an amount to form the single phase. In a first step, an acid catalyst for the esterification of the fatty acids is added. After a period of time, the acid catalyst is neutralized and a base catalyst for the transesterification of triglycerides is added. After a further period of time, esters are separated from the solution.

Claims

1. A single liquid phase process for the esterification of a mixture of fatty acids and triglycerides, comprising:

(a) forming a solution of said fatty acids and triglycerides, an alcohol, an acid catalyst and a cosolvent at a temperature that is less than the boiling point of the solution, said alcohol being selected from the group consisting of methanol, ethanol, and mixtures thereof, and the molar ratio of the alcohol to the triglycerides plus one third of the fatty acids being in the range of 15;

1 to 35;

1, the cosolvent being in an amount to effect formation of a single liquid phase;

(b) maintaining the solution for a period of time to effect acid-catalyzed esterification of the fatty acids;

(c) neutralizing the acid catalyst and adding a base catalyst for the transesterification of the triglycerides; and

(d) after a further period of time, separating esters from said solution.

2. The process of claim 1 in which the solution contains less than 1% by weight of water.

3. The process of claim 2 in which the solution contains less than 0.5% by weight of water.

4. The process of claim 2 in which the alcohol is methanol.

5. The process of claim 2 in which the alcohol is ethanol.

6. The process of claim 2 in which the alcohol is a mixture of ethanol and methanol.

7. The process of claim 2 in which the acid catalyst is anhydrous sulphuric acid.

8. The process of claim 2 in which the base catalyst is selected from sodium hydroxide and potassium hydroxide.

9. The process of claim 7 in which the solution of (a) is neutralized with an alkali metal compound that forms a sulphate.

10. The process of claim 9 in which the alkali metal compound is sodium or potassium carbonate.

11. The process of claim 4 in which the molar ratio of alcohol to fatty acid plus triglyceride is in the range of 20:

1 to 30;

1.

12. The process of claim 11 in which the molar ratio of alcohol to fatty acid plus triglyceride is in the range of 25:

1 to 30;

1.

13. The process of claim 11 in which the triglyceride has fatty acid moieties that are C₁₆ or higher.

14. The process of claim 11 in which the triglyceride is selected from the group consisting of beef tallow, coconut oil, corn oil, cottonseed oil, lard, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, linseed oil, tung oil, sunflower oil, safflower oil, canola oil, rapeseed oil, sesame oil, babassu oil, perilla oil, oiticica oil, fish oils, menhaden oil, castor oil, Chinese tallow tree oil, Physic nut oil, Cuphea seed oil, microalgal oils, bacterial oils and fungal oils.

15. The process of claim 11 in which the cosolvent is a cyclic ether.

16. The process of claim 11 in which the cosolvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether, methyltertiarybutylether and diisopropyl ether.

17. The process of claim 11 in which the temperature is in the range of from 15°

C. to 65°

C.

18. The process of claim 11 in which the temperature is at least 50°

C.

19. The process of claim 11 in which the temperature is at least 60°

C.

20. The process of claim 11 in which ester is recovered in a yield of at least 99%.

21. The process of claim 1 in the form of a continuous process.

22. A biofuel comprising an ester with a glycerol content of less than 0.40% by weight, said ester having been obtained by a process of claim 1.

23. The biofuel of claim 22 in which the glycerol content is less than 0.23% by weight.