Method of making propanol and ethanol from plant material by biological conversion and gasification

• US 8,329,436 B2
• Filed: 02/11/2008
• Issued: 12/11/2012
• Est. Priority Date: 02/09/2007
• Status: Expired due to Fees

• Current Assignee: ZeaChem, Inc.
• Original Assignee: ZeaChem, Inc.
• Inventors: Verser, Dan W., Eggeman, Timothy J.
• Primary Examiner(s): Kosson, Rosanne
• Application Number:
  US12/029,321
• Publication Number:
  US 20080193989A1
• Time in Patent Office: 1,765 Days
• Field of Search: 435/165, 435/161, 435/157, 435/170, 435/141, 435/140
• US Class Current: 435/165
• CPC Class Codes: C12P 7/04 acyclic
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: C12P 7/16 Butanols
• CPC Class Codes: C12P 7/18 polyhydric
• CPC Class Codes: C12P 7/40 containing a carboxyl group including Peroxycarboxylic acids
• CPC Class Codes: C12P 7/44 Polycarboxylic acids
• CPC Class Codes: C12P 7/50 having keto groups, e.g. 2-ketoglutaric acid
• CPC Class Codes: C12P 7/52 Propionic acid; Butyric acids
• 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: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention relates to processes that efficiently convert carbon-containing materials, such as biomass, into products in such a manner that the energy, carbon, and mass content of the materials are efficiently transferred into such products. Such methods include converting the materials into at least one intermediate by a biological conversion process and at least one intermediate by a thermochemical conversion process and reacting the intermediates to form the product. Such methods have a chemical energy efficiency to produce the product that is greater than the chemical energy efficiency of a solely biological conversion process to produce the product and that is greater than the chemical energy efficiency of a process in which all of the material is initially subjected to a thermochemical conversion step as part of the process to produce the product.

Claims

1. A method for producing propanol and ethanol from a material, wherein the material comprises plant material or plant material that has been subject to pretreatment or saccharification, and wherein less than 75% by weight of the carbon-containing compounds in the material are carbohydrate substances, the method comprising:

i) converting the material into at least a first intermediate and a second intermediate,

wherein the first intermediate is produced by a biological conversion process and comprises propionic acid, a propionate ester, a propionate salt, acetic acid, an acetate ester, an acetate salt, or a mixture thereof, and

wherein the second intermediate is produced by gasification and comprises a reductant; and

ii) reacting the reductant and the propionic acid, propionate ester, propionate salt, acetic acid, acetate ester, acetate salt, or a mixture thereof by hydrogenation to produce propanol and ethanol,

wherein the chemical energy efficiency of the method is greater than the chemical energy efficiency of i) a method in which the material is converted into propanol and ethanol using only a biological conversion process; and

ii) a method in which all of the material is initially subjected to a thermochemical conversion step as part of the process to produce propanol and ethanol.

2. The method of claim 1, wherein said reductant is selected from the group consisting of hydrogen, carbon monoxide, and a mixture of hydrogen and carbon monoxide.

3. The method of claim 1, wherein the step of converting comprises

(a) producing propionic acid, a propionate ester, a propionate salt, acetic acid, an acetate ester, an acetate salt, or a mixture thereof by a biological conversion process of carbohydrate substances in the material, and

(b) producing the reductant by gasification of non-carbohydrate substances in the material.

4. The method of claim 1, wherein the biological conversion process comprises fermentation.

5. The method of claim 1, wherein the chemical energy efficiency of the method is at least 60%.

6. The method of claim 1, wherein the chemical energy efficiency of the method is at least 65%.

7. The method of claim 1, wherein the chemical energy efficiency of the method is at least 70%.

8. The method of claim 1, wherein the chemical energy efficiency of the method is at least 75%.

9. The method of claim 1, wherein the chemical energy efficiency of the method is at least 80%.

10. The method of claim 1, wherein the chemical energy efficiency of the method is 82%.

11. The method of claim 1, wherein at least 70% of carbohydrate substances in the material is converted into the product.

12. The method of claim 1, wherein greater than 70% of carbohydrate substances in the material is converted into the product.

13. The method of claim 1, wherein at least 75% of carbohydrate substances in the material is converted into the product.

14. The method of claim 1, wherein at least 80% of carbohydrate substances in the material is converted into the product.

15. The method of claim 1, wherein at least 90% of carbohydrate substances in the material is converted into the product.

16. The method of claim 1, wherein at least 95% of carbohydrate substances in the material is converted into the product.

17. The method of claim 1, wherein 100% of carbohydrate substances in the material is converted into the product.

18. The method of claim 1, wherein only one mole of carbon dioxide is produced per mole of monosaccharide or monosaccharide unit in the material.

19. The method of claim 1, wherein the plant material is selected from the group consisting of herbaceous matter, agricultural residue, forestry residue, municipal solid waste, waste paper, pulp and paper mill residue.

20. The method of claim 1, wherein the plant material is selected from the group consisting of trees, shrubs, grasses, wheat, wheat straw, wheat midlings, sugar cane bagasse, corn, corn husks, corn kernel, corn fiber, municipal solid waste, waste paper, yard waste, branches, bushes, energy crops, fruits, fruit peels, flowers, grains, herbaceous crops, leaves, bark, needles, logs, roots, saplings, short rotation woody crops, switch grasses, vegetables, vines, sugar beet pulp, oat hulls, hard woods, wood chips, intermediate streams from pulping operations and soft woods.

21. The method of claim 1, wherein the plant material is selected from the group consisting of trees, grasses, whole plants, and structural components of plants.

22. The method of claim 1, wherein the biological conversion process comprises fermentation.

23. The method of claim 1, wherein the biological conversion process comprises culturing at least one microorganism.

24. The method of claim 23, wherein the biological conversion process comprises culturing at least one homofermentative microorganism.

25. The method of claim 23, wherein the at least one microorganism is selected from the group consisting of homoacetogenic microorganisms, homolactic microorganisms, propionic acid bacteria, butyric acid bacteria, succinic acid bacteria and 3-hydroxypropionic acid bacteria.

26. The method of claim 23, wherein the at least one microorganism is of a genus selected from the group consisting of Clostridium, Lactobacillus, Moorella, Thermoanaerobacter, Propionibacterium, Propionispera, Anaerobiospirillum, and Bacteriodes.

27. The method of claim 23, wherein the at least one microorganism is of a species selected from the group consisting of Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbrukii, Propionibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum succinicproducens, Bacteriodes amylophilus and Bacteriodes ruminicola.

28. The method of claim 1, wherein the at least one thermochemical process-produced intermediate is selected from the group consisting of syngas, a component of syngas, a mixture of syngas components, pyrolysis gas, a component of pyrolysis gas, and a mixture of pyrolysis gas components.

29. The method of claim 1, wherein the at least one thermochemical process-produced intermediate is selected from the group consisting of hydrogen, carbon monoxide, carbon dioxide, and methanol.

30. The method of claim 1, wherein if the at least one biological process-produced intermediate comprises a salt of a carboxylic acid, the method further comprises acidifying the salt of the carboxylic acid to form the carboxylic acid prior to the step of reacting.

31. The method of claim 30, further comprising esterifying the carboxylic-acid prior to the step of reacting.

32. The method of claim 30, wherein the step of acidifying comprises introducing carbon dioxide, or an acid with a lower pKa than the carboxylic-acid of the intermediate being acidified, to a solution comprising the salt of the carboxylic acid.

33. The method of claim 30, wherein said step of acidifying comprises introducing a tertiary amine with carbon dioxide to form an acid/amine complex.

34. The method of claim 33, further comprising contacting the acid/amine complex with a water immiscible solvent to form an ester of the water immiscible solvent and the carboxylic acid.

35. The method of claim 1, wherein the step of reacting the at least one biological process-produced intermediate and the at least one thermochemical process-produced intermediate is a process of reduction to produce the product.

36. The method of claim 1, further comprising fractionating the material to form a carbohydrate-containing fraction, which is used to produce the first intermediate, and a residue fraction comprising lignin, which is used to produce the second intermediate.

37. The method of claim 36, wherein the step of fractionating is selected from the group consisting of physical treatment, metal ion treatment, ultraviolet light treatment, ozone treatment, oxygen treatment, organosolv treatment, steam explosion treatment, lime impregnation with steam explosion treatment, lime impregnation without steam treatment, hydrogen peroxide treatment, hydrogen peroxide/ozone (peroxone) treatment, acid treatment, dilute acid treatment, and base treatment.

38. The method of claim 1,

(a) wherein the at least one biological process-produced intermediate is produced by fermentation of carbohydrate substances in the material,

(b) wherein the at least one thermochemical process-produced intermediate is produced by thermochemical conversion of non-carbohydrate substances in the material, and

(c) wherein the at least one biological process-produced intermediate of (a) and the at least one thermochemical process-produced intermediate of (b) are chemically reacted to produce the product.

39. The method of claim 1,

(a) wherein the material is fermented to produce at least one biological process-produced intermediate and a fermentation residue comprising non-fermented components of the material,

(b) wherein the at least one thermochemical process-produced intermediate is produced by thermochemical conversion of the fermentation residue, and

(c) wherein the at least one biological process-produced intermediate of (a) and the at least one thermochemical process-produced intermediate of (b) are chemically reacted to produce the product.