Method of converting free fatty acids to fatty acid methyl esters with small excess of methanol

• US 6,965,044 B1
• Filed: 07/05/2002
• Issued: 11/15/2005
• Est. Priority Date: 07/06/2001
• Status: Expired due to Fees

• Current Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Original Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Inventors: Wang, Tong, Hammond, Earl G.
• Primary Examiner(s): Carr, Deborah D.
• Application Number:
  US10/190,771
• Time in Patent Office: 1,229 Days
• Field of Search: 554/156, 554/167, 554/169
• US Class Current: 554/169
• 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 method for converting free fatty acids in acid oil or acid fat into fatty acid methyl esters is disclosed. The method involves adding a small amount of methanol and an acid catalyst to the acid oil or acid fat and subjecting the mixture to conditions that allow the fatty acid methyl esters to form. A lipid phase containing the fatty acid methyl esters and triglycerides can from and be separated from the rest of the reaction mixture. The lipid phase can then be subjected to conditions suitable for converting the triglycerides into fatty acid methyl esters. The method of present invention is especially useful for a process of generating biodiesel using a starting material of vegetable and animal oils and fats that contain a relatively high level of free fatty acids.

Claims

1. A method for converting free fatty acids in acid oil or acid fat to fatty acid methyl esters comprising the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat; and

subjecting mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids, wherein, after performing the subjecting step, any glycerol in the mixture was formed in the method.

2. The method of claim 1, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

3. The method of claim 1, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

4. The method of claim 1, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

5. The method of claim 1, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

6. The method of claim 1, wherein the catalyst is sulfuric acid.

7. The method of claim 1, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

8. A method for preparing acid oil or acid fat for transesterification reactions to convert triglycerides to fatty acid methyl esters, the method comprising the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat;

subjecting mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids, wherein, after performing the subjecting step, any glycerol in the mixture was formed in the method;

subjecting the mixture containing fatty acid methyl esters to conditions suitable for forming a separate lipid phase from the rest of the mixture wherein the lipid phase contains oil or fat and fatty acid methyl esters; and

recovering the lipid phase.

9. The method of claim 8, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

10. The method of claim 8, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

11. The method of claim 8, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

12. The method of claim 8, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

13. The method of claim 8, wherein the catalyst is sulfuric acid.

14. The method of claim 8, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

15. A method for producing fatty acid methyl esters from acid oil or acid fat comprising the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat;

subjecting mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids, wherein, after performing the subjecting step, any glycerol in the mixture was formed in the method;

subjecting the mixture containing fatty acid methyl esters to conditions suitable for forming a separate lipid phase from the rest of the mixture wherein the lipid phase contains oil or fat and fatty acid methyl esters;

recovering the lipid phase; and

converting triglycerides in the lipid phase to fatty acid methyl esters.

16. The method of claim 15, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

17. The method of claim 15, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

18. The method of claim 15, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

19. The method of claim 15, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

20. The method of claim 15, wherein the catalyst is sulfuric acid.

21. The method of claim 15, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

22. The method of claim 15, wherein the triglycerides in the lipid phase are converted to fatty acid methyl esters using an acid catalyst.

23. The method of claim 15, wherein the triglycerides in the lipid phase are converted to fatty acid methyl esters using a base catalyst.

24. A method for converting free fatty acids in acid oil or acid fat to fatty acid methyl esters consisting essentially of the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat; and

subjecting the mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids.

25. The method of claim 24, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

26. The method of claim 24, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

27. The method of claim 24, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

28. The method of claim 24, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

29. The method of claim 24, wherein the catalyst is sulfuric acid.

30. The method of claim 24, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

31. A method for preparing acid oil or acid fat for transesterification reactions to convert triglycerides to fatty acid methyl esters, the method consisting essentially of the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat;

subjecting the mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids;

subjecting the mixture containing fatty acid methyl esters to conditions suitable for forming a separate lipid phase from the rest of the mixture wherein the lipid phase contains oil or fat and fatty acid methyl esters; and

recovering the lipid phase.

32. The method of claim 31, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

33. The method of claim 31, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

34. The method of claim 31, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

35. The method of claim 31, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

36. The method of claim 31, wherein the catalyst is sulfuric acid.

37. The method of claim 31, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

38. A method for producing fatty acid methyl esters from acid oil or acid fat consisting essentially of the steps of:

determining the free fatty acid level in the acid oil or acid fat;

adding methanol into the acid oil or oil fat in an amount about 100% to about 470% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters;

adding an acid catalyst for esterification reaction into the acid oil or acid fat;

subjecting the mixture of acid oil or acid fat, methanol and the catalyst to conditions suitable for forming fatty acid methyl esters so that fatty acids methyl esters form from the free fatty acids;

subjecting the mixture containing fatty acid methyl esters to conditions suitable for forming a separate lipid phase from the rest of the mixture wherein the lipid phase contains oil or fat and fatty acid methyl esters;

recovering the lipid phase; and

converting triglycerides in the lipid phase to fatty acid methyl esters.

39. The method of claim 38, wherein the methanol added into the acid oil or acid fat is about 120% to about 300% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

40. The method of claim 38, wherein the methanol added into the acid oil or acid fat is about 270% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

41. The method of claim 38, wherein the methanol added into the acid oil or acid fat is between 100% and 150% of the theoretical amount needed to convert all free fatty acids in the acid oil or acid fat into methyl esters.

42. The method of claim 38, wherein the catalyst is selected from sulfuric acid, hydrogen chloride and p-toluenesulfonic acid.

43. The method of claim 38, wherein the catalyst is sulfuric acid.

44. The method of claim 38, wherein the conditions suitable for forming fatty acid methyl esters are reflux reaction conditions.

45. The method of claim 38, wherein the triglycerides in the lipid phase are converted to fatty acid methyl esters using an acid catalyst.

46. The method of claim 38, wherein the triglycerides in the lipid phase are converted to fatty acid methyl esters using a base catalyst.