Process for manufacturing ethanol and for recovering glycerol, succinic acid, lactic acid, betaine, potassium sulfate, and free flowing distiller's dry grain and solubles or a solid fertilizer therefrom

• US 5,177,008 A
• Filed: 06/18/1990
• Issued: 01/05/1993
• Est. Priority Date: 12/22/1987
• Status: Expired due to Fees

• Current Assignee: Willem H. Kampen
• Original Assignee: Willem H. Kampen
• Inventors: Kampen, Willem H.
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): McMahon, Timothy M.
• Application Number:
  US07/537,779
• Time in Patent Office: 932 Days
• Field of Search: 435/139, 435/141, 435/145, 435/146, 435/159, 435/161, 435/163
• US Class Current: 435/139
• CPC Class Codes: C12F 3/10 from distillery slops
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: C12P 7/20 Glycerol
• CPC Class Codes: C12P 7/46 Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

This invention relates to the manufacture of ethanol and the recovery of economically significant amounts of such by-products therefrom as glycerol, betaine, L-pyroglutamic acid, succinic and lactic acid, potassium sulfate and a free flowing distiller'"'"'s dry grain and solubles useful as an animal feed or a component of food for humans or as a premix for agricultural fertilizer and/or a feed additive. An important aspect of the recovery step is the utilization of a crossflow microfiltration system which includes inorganic membranes for the classification of the stillage.

Claims

1. A continuous process for recovering glycerol from stillage produced from the fermentation and distillation of such biological materials as corn, wheat, other grains, sugar cane, sugar beets, grapes, other fruit, potatoes, cassava, sweet sorghum, and the like which results in ethanol and said stillage, said continuous process comprising the steps of

a) clarifying the stillage by subjecting the stillage to a cross-flow microfiltration process utilizing inorganic membranes having pore sizes in the range of 0.1 to 10 microns.

b) passing the clarified stillage through an ion exclusion material for separating chromatographically glycerol from other constituents of the clarified stillage, and

c) purifying the separated glycerol.

2. The process according to claim 1 wherein the step of clarifying further comprises initially centrifugally separating solids from liquid constituents prior to subjecting the stillage to microfiltration.

3. The process according to claim 1 wherein when sugar beets are used as the stillage producing material, the clarified stillage from step (a) is enzymatically treated to hydrolize proteinaceous material.

4. The process according to claim 1 wherein when sugar beets are used as the stillage producing materials, the clarified stillage is concentrated to 50-75% solids and the resulting potassium sulfate crystals are removed.

5. The process according to claim 1 wherein the permeate from the microfiltration step is concentrated to as high a solids concentration as practicable before passing through said ion exclusion material.

6. The process according to claim 1 wherein said purifying step comprises the steps of ion exchange, evaporation to a concentration of 80-85% glycerol, further distillation and refining into glycerol having a purity of at least 99.7%.

7. The process according to claim 1 wherein said stillage is produced by the steps of:

a) preparing a mash from biological materials;

b) fermenting said mash with sufficient yeast to produce a fermented mash having at least about 9 grams of glycerol and 40 grams of ethanol per 100 grams of reducing sugar in the mash;

c) distilling the fermented mash to produce ethanol in said stillage.

8. The process according to claim 7 wherein said yeast comprises immobilized yeast cells.

9. The process according to claim 7 wherein said step of fermenting said mash comprises the step of mixing with said mash yeast cells in a concentration in excess of 100 grams per liter.

10. The process according to claim 7 wherein said mash is so prepared as to have a dextrose equivalent of at least about 80.

11. The process according to claim 7 wherein the pH of the mash is maintained substantially constant during the first two-thirds of said fermentation process.

12. The process according to claim 7 wherein the step of fermenting said mash comprises adding sufficient yeast to produce a fermented mash having at least about 15 grams of glycerol and 40 grams of ethanol per 100 grams of reducing sugar in the mash.

13. The process according to claim 7 wherein said steps of clarifying, chromatographic separation, and purifying are a continuous process.

26. Glycerol manufactured in accordance with the process of claim 1.

14. A continuous process for recovering glycerol and betaine from stillage produced from the fermentation and distillation of sugar beets which results in ethanol and said stillage, said continuous process comprising the steps of:

a) clarifying said stillage by subjecting the stillage to a cross-flow microfiltration process utilizing inorganic membranes having pore sizes in the range of 0.1-10 microns;

b) subjecting the clarified stillage to a first chromatographic separation by passing the clarified stillage through an ion-exclusion apparatus for separating glycerol and betaine as a mixture from other constituents of the clarified stillage;

c) subjecting the glycerol/betaine mixture to a second chromatographic separation by passing the mixture through a second ion exclusion apparatus in which the glycerol is separated from the betaine; and

d) purifying the separated glycerol and betaine.

15. The process according to claim 14 wherein said step of clarifying further comprises initially centrifugally separating solids from liquid constituents prior to subjecting the stillage to microfiltration.

16. The process according to claim 14 wherein the clarified stillage from step (a) is enzymatically treated to hydrolize proteinaceous material.

17. The process according to claim 14 wherein the clarified stillage is concentrated to 50-75% solids and the resulting potassium sulfate crystals are removed.

18. The process according to claim 14 wherein the glycerol/betaine stream from the first chromatographic separation step is concentrated to approximately 75 wt. percent before passing onto the second chromatographic separation step.

19. The process according to claim 14 wherein the glycerol stream and the betaine stream which issue from the second chromatographic separation step are each subjected to ion exchange, further concentration, and purification by distillation and refining into glycerol and crystallization into betaine-HCl or betaine.

20. The process according to claim 14 wherein the permeate from the clarification step is subjected to a crystallization process resulting in potassium sulfate crystals and a permeate containing glycerol/betaine which is passed on to said first chromatographic separation step.

21. The process according to claim 14 wherein said first chromatographic separation separates essentially glycerol and betaine into a first stream and a second stream contains other products including at least one of such products as succinic acid, lactic acid and L-pyroglutamic acid, and said second stream is subjected to further chromatographic separation stages to separate each, all and any combination of the other products from the remaining products.

22. The process according to claim 14 wherein said fermentation, distillation, clarification, chromatographic separation, and purification are all a part of a continuous process.

27. Glycerol and betaine manufactured in accordance with the process of claim 14.

28. Glycerol, betaine and potassium sulfate manufactured in accordance with the process of claim 14.

29. Glycerol betaine, and L-pyroglutamic acid manufactured in accordance with the process of claim 14.

23. A continuous process for recovering at least two of the group containing glycerol, betaine, succinic acid, lactic acid, L-pyroglutamic acid from stillage produced from the fermentation and distillation of such biological materials as corn, wheat, other grain, sugar cane, sugar beets, grapes, other fruit, potatoes, cassava, sweet sorghum, and the like which result in ethanol and said stillage, said continuous process comprising the steps of:

a) clarifying the stillage produced from the distillation of the fermented mash by subjecting the stillage to a cross-flow microfiltration process utilizing inorganic membranes having pore sizes in the range of 0.1-10 microns;

b) passing the clarified stillage through a succession of ion exclusion apparatuses for chromatographically and/or physico-chemically separating each product from the other constituents of the clarified stillage; and

c) purifying the separated product.

24. The process according to claim 23 wherein when sugar beets are used as the stillage producing material, the clarified stillage from step (a) is enzymatically treated to hydrolize proteinaceous material.

25. The process according to claim 23 wherein when sugar beets are used as the stillage producing material, the clarified stillage is concentrated to 50-75% solids and the resulting potassium sulfate crystals are removed.

30. Glycerol and one of the group consisting of betaine, succinic acid, lactic acid, and L-pyroglutamic acid manufactured in accordance with the process of claim 23.

31. A continuous process for the recovery of betaine from beet stillage produced from the fermentation and distillation of sugar beets which results in ethanol and said beet stillage, the continuous process comprising the steps of:

a) clarifying said stillage produced from the distillation of fermented sugar beet mash by subjecting the stillage to a cross-flow microfiltration process utilizing inorganic membranes having pore sizes in the range of 0.1-10 microns;

b) subjecting the clarified stillage to chromatographic separation by passing the clarified stillage through an ion exclusion apparatus for separating betaine from other constituents of the clarified stillage; and

c) purifying the separated betaine.

32. The process according to claim 31 wherein the step of clarifying further comprises initially centrifugally separating solids from liquid constituents prior to subjecting the stillage to microfiltration.

33. The process according to claim 31 wherein the clarified stillage from step (a) is enzymatically treated to hydrolize proteinaceous material.

34. The process according to claim 31 wherein the clarified stillage is concentrated to 50-75% solids and the resulting potassium sulfate crystals are removed.

35. The process according to claim 31 wherein the permeate from the microfiltration step is concentrated to as high a solids concentration as practicable before passing through said ion exclusion material.

36. The process according to claim 31 wherein said purifying step comprises the steps of ion exchange, evaporation to a concentration of 80-85% glycerol, further distillation and refining into glycerol having a purity of at least 99.7%.

37. The process according to claim 31 wherein said clarification, chromatographic separation, and purification are all a part of a continuous process.