Process for producing ethanol

• US 6,927,048 B2
• Filed: 12/04/2002
• Issued: 08/09/2005
• Est. Priority Date: 03/11/1999
• Status: Expired due to Term

• Current Assignee: ZeaChem, Inc.
• Original Assignee: ZEA Chem Incorporated
• Inventors: Verser, Dan, Eggeman, Tim
• Primary Examiner(s): Lilling, Herbert J.
• Application Number:
  US10/310,552
• Publication Number:
  US 20030077771A1
• Time in Patent Office: 979 Days
• Field of Search: 435/161, 435/162
• US Class Current: 435/161
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/08 Ethanol
• 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 69/14 of monohydroxylic compounds
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: C12P 7/14 Multiple stages of fermentation; Multiple types of microorganisms or re-use of microorganisms
• CPC Class Codes: C12P 7/54 Acetic acid vinegar C12J
• CPC Class Codes: C12P 7/56 Lactic acid
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

A process for producing ethanol including a combination of biochemical and synthetic conversions results in high yield ethanol production with concurrent production of high value coproducts. An acetic acid intermediate is produced from carbohydrates, such as corn, using enzymatic milling and fermentation steps, followed by conversion of the acetic acid into ethanol using esterification and hydrogenation reactions. Coproducts can include corn oil, and high protein animal feed containing the biomass produced in the fermentation.

Claims

1. A method to produce ethanol, comprising:

(a) fermenting a medium comprising a carbohydrate source into acetate, acetic acid or mixtures thereof;

(b) esterifying said acetate, acetic acid or mixtures thereof to an acetic acid ester in the presence of an alcohol; and

(c) hydrogenating said acetic acid ester to said ethanol and said alcohol, wherein hydrogen for said step of hydrogenating is produced by a method selected from the group consisting of steam reforming, water electrolysis, gasification from biomass, partial oxidation of hydrocarbons, and partial oxidation of coal.

2. The method of claim 1, wherein said alcohol produced in step (c) is recycled to said step (b).

3. The method of claim 1, wherein said step of esterifying is accomplished by reactive distillation.

4. The method of claim 1, wherein said alcohol is ethanol and said acetic acid ester is ethyl acetate.

5. The method of claim 1, wherein said acetic acid is produced by acidifying acetate salt produced during said step of fermenting.

6. The method of claim 5, wherein said step of acidifying comprises:

(i) reaction of acetate salt with carbonic acid and an amine to form calcium carbonate and an amine complex of the acetate;

(ii) recovery of the amine complex and thermal decomposition to regenerate the amine and form acetic acid; and

(iii) recovery of the calcium carbonate.

7. The method of claim 6, wherein calcium carbonate produced as part of said step of acidifying is recycled into said step of fermenting.

8. A method to produce ethanol, comprising:

(a) culturing in a fermentation medium comprising a carbohydrate source a homoacetogenic microorganism to produce acetate, acetic acid or mixtures thereof;

(b) esterifying said acetate, acetic acid or mixtures thereof to an acetic acid ester in the presence of an alcohol; and

(c) hydrogenating said acetic acid ester to said ethanol and said alcohol.

9. The method of claim 8, wherein said homoacetogenic microorganism is a microorganism of the genus Clostridium.

10. The method of claim 8, wherein said homoacetogenic microorganism is a microorganism of the species Clostridium thermoaceticum or Clostridium formicoaceticum.

11. The method of claim 8, wherein said alcohol produced in step (c) is recycled to said step (b).

12. The method of claim 8, wherein said step of esterifying is accomplished by reactive distillation.

13. The method of claim 8, wherein said alcohol is ethanol and said acetic acid ester is ethyl acetate.

14. The method of claim 8, wherein hydrogen for said step of hydrogenating is produced by a method comprising steam reforming.

15. The method of claim 14, wherein said method of steam reforming comprises reacting methane and water to produce carbon dioxide and hydrogen.

16. The method of claim 8, wherein hydrogen for said step of hydrogenating is produced from a renewable source.

17. The method of claim 8, wherein hydrogen for said step of hydrogenating is produced from biomass.

18. The method of claim 18, wherein said acetic acid is produced by acidifying acetate salt produced during said step of fermenting.

19. The method of claim 18, wherein said step of acidifying comprises:

(i) reaction of acetate salt with carbonic acid and an amine to form calcium carbonate and an amine complex of the acetate;

(ii) recovery of the amine complex and thermal decomposition to regenerate the amine and form acetic acid; and

(iii) recovery of the calcium carbonate.

20. The method of claim 19, wherein calcium carbonate produced as part of said step of acidifying is recycled into said step of fermenting two moles lactate and the lactate is converted to about three moles acetate.