Process for producing ethanol from corn dry milling

• US 7,507,562 B2
• Filed: 01/24/2006
• Issued: 03/24/2009
• Est. Priority Date: 03/11/1999
• Status: Expired due to Fees

• Current Assignee: ZeaChem, Inc.
• Original Assignee: ZeaChem, Inc.
• Inventors: Verser, Dan W., Eggeman, Timothy J.
• Primary Examiner(s): Lilling; Herbert J.
• Application Number:
  US11/339,238
• Publication Number:
  US 20060127999A1
• Time in Patent Office: 1,155 Days
• Field of Search: None
• US Class Current: 435/135
• CPC Class Codes: B01D 3/002 by continuous methods
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/08 Ethanol
• 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 7/62 Carboxylic acid esters
• 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 by the conversion of carbohydrates from a corn dry milling process in which the bottoms fraction from distillation of ethanol in a conventional yeast fermentation is used in a process including a combination of biochemical and synthetic conversions. The process results in high yield ethanol production with concurrent production of high value coproducts. An acetic acid intermediate is produced from bottoms fraction, followed by conversion of the acetic acid into ethanol using esterification and hydrogenation reactions. Coproducts of the process include a high protein content solids fraction produced in the fermentation.

Claims

1. A process for the production of an ester of acetic acid, comprising:

a. conducting a yeast fermentation in a corn preparation to produce ethanol;

b. distilling the ethanol from the yeast fermentation to produce a bottoms fraction;

c. hydrolyzing the bottoms fraction;

d. separating the hydrolyzed bottoms fraction into a solids fraction and a liquid hydrolyzate;

e. culturing a homofermentative microorganism in the liquid hydrolyzate to produce acetate, acetic acid or mixtures thereof; and

f. chemically convening the acetate, acetic acid or mixtures thereof to an ester of acetic acid.

2. The process, as claimed in claim 1, wherein the step of hydrolyzing comprises hot water pretreatment of the bottoms fraction.

3. The process, as claimed in claim 1, wherein the step of hydrolyzing comprises enzymatic hydrolysis.

4. The process, as claimed in claim 1, wherein the step of hydrolyzing comprises contacting the bottoms fraction with xylanase and cellulase enzymes.

5. The process, as claimed in claim 1, wherein the solids fraction comprises a majority of protein from the corn.

6. The process, as claimed in claim 1, wherein the solids fraction comprises at least about 35% protein on a dry weight basis.

7. The process, as claimed in claim 1, wherein the solids fraction comprises the lipid fraction from the corn.

8. The process, as claimed in claim 1, wherein the volume of the solids fraction is about one-half the volume of distiller'"'"'s dried grains and solubles (DDGS) produced by the same volume of corn preparation.

9. The process, as claimed in claim 1, further comprising the step of drying the solids fraction.

10. The process, as claimed in claim 9, wherein the step of drying is conducted with a dryer suitable for producing DDGS from a bottoms fraction.

11. The process, as claimed in claim 9, wherein the step of drying is conducted without a pre-step of separating and concentrating a liquid portion of the solids fraction.

12. The process, as claimed in claim 1, wherein the fermentable fraction of the liquid hydrolysate is less than about 6% by weight.

13. The process, as claimed in claim 1, wherein at least about 70% of carbon in the bottoms fraction is converted into ethanol.

14. The process, as claimed in claim 1, wherein the homofermentative microorganism is a homoacetogenic microorganism.

15. The process, as claimed in claim 14, wherein the homoacetogenic microorganism is of the species Clostridium thermoaceticum or Clostridium formicoaceticum.

16. The process, as claimed in claim 1, wherein said step of culturing comprises:

(i) converting by fermentation the liquid hydrolyzate into lactic acid, lactate or mixtures thereof; and

(ii) converting by fermentation lactic acid, lactate or mixtures thereof into acetic acid, acetate or mixtures thereof.

17. The process, as claimed in claim 16, wherein said step (i) comprises a homolactic fermentation.

18. The process, as claimed in claim 17, wherein said homolactic fermentation is accomplished by a microorganism of the genus Lactobacillus.

19. The process, as claimed in claim 16, wherein said step (ii) comprises a homoacetic fermentation.

20. The process, as claimed in claim 19, wherein said homoacetic fermentation is accomplished by a microorganism of the genus Clostridium.

21. The process, as claimed in claim 1, wherein step (f) comprises:

(i) esterifying said acetic acid to an acetic acid ester in the presence of an alcohol; and

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

22. The process, as claimed in claim 21, wherein said alcohol produced in step (ii) is recycled to said step (i).

23. The process, as claimed in claim 21, wherein said alcohol in step (i) comprises ethanol produced by the yeast fermentation of step (a).

24. The process, as claimed in claim 1, further comprising:

a. acidifying said acetate with carbon dioxide to produce acetic acid and calcium carbonate;

b. esterifying said acetic acid with an alcohol to form an ester; and

c. recovering said ester.

25. The process, as claimed in claim 24, wherein said ester is recovered by distillation.

26. The process, as claimed in claim 25, wherein said distillation is a reactive distillation capable of pushing the acidification and esterification equilibria to high conversion to the desired ester product.

27. The process, as claimed in claim 24, wherein said ester is converted to ethanol.

28. The process, as claimed in claim 1, wherein said ester of acetic acid is ethyl acetate.

29. The process, as claimed in claim 1, further comprising contacting the bottoms fraction with a protease.

30. A process for upgrading the unfermented fraction of corn from a yeast fermentation based corn dry milling ethanol process, comprising:

a. hydrolyzing a bottoms fraction produced by distilling ethanol from the yeast fermentation;

b. separating the hydrolyzed bottoms fraction into a solids fraction and a liquid hydrolyzate;

c. culturing a homofermentative microorganism in the liquid hydrolyzate to produce acetate, acetic acid or mixtures thereof; and

d. chemically converting the acetate, acetic acid or mixtures thereof to a product selected from the group consisting of ethanol and ethyl acetate.

31. A process for the production of an ester of acetic acid, comprising:

a. culturing a homofermentative microorganism in a liquid hydrolysate to produce acetate, acetic acid or mixtures thereof, wherein the liquid hydrolysate is a liquid fraction of a hydrolysate of a bottoms fraction resulting from distilling ethanol from a yeast fermentation; and

b. chemically convening the acetate, acetic acid or mixtures thereof to an ester of acetic acid.