Process for the hydrolysis of starch and the continuous fermentation of the sugars obtained therefrom to provide ethanol

• US 4,243,750 A
• Filed: 05/29/1979
• Issued: 01/06/1981
• Est. Priority Date: 05/29/1979
• Status: Expired due to Term

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: National Distillers and Chemical Corporation
• Inventors: Miller, Franklyn D., Muller, Werner C.
• Primary Examiner(s): Shapiro, Lionel M.
• Application Number:
  US06/043,193
• Time in Patent Office: 588 Days
• Field of Search: 435/161-165, 435/813, 435/940, 435/42, 435/96, 435/99
• US Class Current: 435/162
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: C13K 1/06 obtained by saccharification of starch or raw materials containing starch
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y10S 435/813 Continuous fermentation
• CPC Class Codes: Y10S 435/94 Saccharomyces

Abstract

Starch is converted to ethanol by a process in which an aqueous starch slurry is hydrolyzed in sequential liquefication and saccharification steps to provide sterile saccharified starch solution containing from about 60 to about 80 weight percent of fermentable sugar based on the weight of the original starch present and the fermentable sugar is thereafter continuously converted by fermentation to dilute aqueous ethanol ("beer") in a series of agitated fermentation vessels which contain progressively more ethanol and less fermentable sugar employing at least two strains of yeast for the fermentation, one of which provides a high rate of ethanol production in a fermentation medium containing a relatively low concentration of ethanol and a relatively high concentration of fermentable sugar and the other of which provides a high rate of ethanol production in a fermentation medium containing a relatively high concentration of ethanol and a relatively low concentration of fermentable sugar.

Claims

1. A process for the hydrolysis of starch and the continuous fermentation of the fermentable sugars therefrom to provide ethanol which comprises:

(a) liquefying an aqueous slurry of starch in the presence of a liquefying agent selected from the group consisting of strong acid and liquefying enzyme to provide sterile liquefied starch;

(b) saccharifying the sterile liquefied starch in a primary saccharification vessel or vessels in the presence of a saccharifying enzyme to provide an aqueous solution of sterile saccharified starch containing from about 60 to about 80 weight percent of the original starch in the form of fermentable sugar, the remaining portion of the starch being present in the form of partial hydrolysate; and

,

(c) continuously fermenting the fermentable sugar, with or without partial hydrolysate therein having been previously further saccharified in a secondary saccharification vessel or vessels, in a series of fermentation vessels in which the ethanol content of the fermentation medium is progressively increased in each fermentation vessel as the fermentable sugar is consumed therein, the fermentation employing at least two different strains of ethanol-producing yeast, one of which provides a high rate of ethanol production in a fermentation medium containing a relatively low concentration of ethanol and a relatively high concentration of sugar and the other of which provides a high rate of ethanol production in a fermentation medium containing a relatively high concentration of ethanol and a relatively low concentration of fermentable sugar.

2. The process of claim 1 wherein the starch is derived from manioc root.

3. The process of claim 2 wherein the hydrogen cyanide generated from the hydrolysis of cyanogenic glucosides during the liquefaction of the starch is substantially eliminated therefrom.

4. The process of claim 1 wherein the starch contains water soluble protein, fat, sugar, vitamins, and/or minerals.

5. The process of claim 1 wherein the starch contains water insoluble components which are removed prior to the consumption of the saccharified starch.

6. The process of claim 1 wherein strong acid is used exclusively to achieve liquefaction.

7. The process of claim 6 wherein the strong acid is at least one member of the group consisting of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.

8. The process of claim 7 wherein ammonia or aqueous ammonia is added to the liquefied starch to at least partially neutralize the acid and form at least one salt selected from the group consisting of ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium phosphate.

9. The process of claim 8, wherein the pH of the neutralized liquefied starch is adjusted to from about 4.0 to about 5.0 prior to the addition of saccharifying enzyme.

10. The process of claim 9, wherein the pH of the neutralized liquefied starch is adjusted from about 4.3 to about 4.7 prior to the addition of saccharifying enzyme.

11. The process of claim 1 wherein liquefying enzyme is used exclusively to achieve liquefaction.

12. The process of claim 11 wherein the pH of the aqueous starch slurry is adjusted to from about 3.0 to about 6.0 prior to, with, or following the addition of liquefying enzyme but before significant liquefaction has occurred.

13. The process of claim 11 wherein the pH of the aqueous starch slurry is adjusted to from about 4.0 to about 5.0 prior to, with, or following the addition of liquefying enzyme but before significant liquefaction has occurred.

14. The process of claim 12 wherein the pH is adjusted by use of a strong acid.

15. The process of claim 17 wherein the strong acid is selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.

16. The process of claim 11 wherein the liquefying enzyme is alpha-amylase.

17. The process of claim 11 wherein only as much liquefying enzyme is added to the aqueous starch slurry prior to initial liquefaction as is necessary to provide a pumpable starch fluid following initial liquefaction, the remaining portion of the liquefying enzyme then being added to further liquefaction.

18. The process of claim 17 wherein from about 1/4 to about 1/3 of the total amount of liquefying enzyme is added to the aqueous starch slurry to initiate liquefaction and from about 3/4 to 2/3 of the total amount of liquefying enzyme is added to the initially liquefied starch to further liquefaction.

19. The process of claim 11, wherein the pH of the liquefied starch is adjusted, if necessary, to from about 4.0 to about 5.0 prior to the addition of saccharifying enzyme.

20. The process of claim 19, wherein the pH of the liquefied starch is adjusted, if necessary, to from about 4.3 to about 4.7 prior to the addition of saccharifying enzyme.

21. The process of claim 1 wherein strong acid is first used to accomplish initial liquefaction and liquefying enzyme is subsequently used to further liquefaction.

22. The process of claim 21 wherein the strong acid is at least one member of the group consisting of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid and the liquefying enzyme is alpha-amylase.

23. The process of claim 22 wherein ammonia or aqueous ammonia is added to the initially liquefied starch prior to the addition of liquefying enzyme to at least partially neutralize the acid and form at least one salt selected from the group consisting of ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium phosphate.

24. The process of claim 1 wherein the saccharifying enzyme is amyloglucosidase.

25. The process of claim 1 wherein further saccharification is carried out in a secondary saccharification vessel or vessels having a total volume of at least V₂ =V₁ x/y wherein V₁ is the total volume of the fermentation medium in the primary saccharification vessel or vessels, x is the period of saccharification in the secondary saccharification vessel or vessels and y is the period of saccharification in the primary saccharification vessel or vessels.

26. The process of claim 1 wherein the aqueous solution of fermentable sugar contains partial starch hydrolysate in an amount of up to about 40 weight percent of the total carbohydrate present, the partial starch hydrolysates undergoing saccharification to fermentable sugar in one or more fermentation vessels in the series under the influence of saccharifying enzyme produced by the yeast and/or added saccharifying enzyme.

27. The process of claim 1 wherein the strain of yeast which provides a high rate of ethanol production in a fermentation medium containing a relatively low concentration of ethanol and a relatively high concentration of sugar is Saccharomyces bayanus.

28. The process of claim 1 wherein the strain of yeast which provides a high rate of ethanol production in a fermentation medium containing a relatively high concentration of ethanol and a relatively low concentration of sugar is Saccharomyces cerevisiae.

29. The process of claim 1 wherein each different strain of yeast is separately employed in a fermentation vessel and is separately recovered therefrom and recycled thereto.

30. The process of claim 1 wherein the different strains of yeast are used together in each fermentation vessel and are separated from the last fermentation vessel in the series and recycled to the first fermentation vessel in the series.

31. The process of claim 1 wherein ethanol contained in the carbon dioxide gas evolved during fermentation is recovered.

32. The process of claim 1 wherein from 2 to 8 weight percent of yeast calculated on a dry yeast basis is present in each fermentation vessel.

33. The process of claim 32 wherein from 3 to 6 weight percent of yeast calculated on a dry yeast basis is present in each fermentation vessel.

34. The process of claim 1 wherein the aqueous solution of fermentable sugar contains from about 10 to about 40 weight percent sugar.

35. The process of claim 34 wherein the aqueous solution of fermentable sugar contains from about 15 to 25 weight percent sugar.

36. A process for the hydrolysis of starch and the continuous fermentation of the fermentable sugars therefrom to provide ethanol which comprises:

(a) liquefying an aqueous slurry of starch in the presence of a liquefying agent selected from the group consisting of strong acid and liquefying enzyme to provide sterile liquefied starch;

(b) saccharifying the liquefied starch in a primary saccharification vessel or vessels in the presence of a saccharifying enzyme for from about two to about ten hours to provide sterile saccharified starch containing from about 60 to about 80 weight percent of the original starch in the form of fermentable sugar, the remaining portion of the starch being present in the form of partial hydrolysate; and

(c) continuously fermenting the fermentable sugar, with or without partial hydrolysate therein having been previously further saccharified in a secondary saccharification vessel or vessels, in a series of fermentation vessels in which the ethanol content of the fermentation medium is progressively increased in each fermentation vessel as the fermentable sugar is consumed therein, the fermentation employing at least two different strains of ethanol-producing yeast, one of which provides a high rate of ethanol production in a fermentation medium containing a relatively low concentration of ethanol and a relatively high concentration of sugar and the other of which provides a high rate of ethanol production in a fermentation medium containing a relatively high concentration of ethanol and a relatively low concentration of fermentable sugar.