WO2009100434A1 - Indirect production of butanol and hexanol - Google Patents
Indirect production of butanol and hexanol Download PDFInfo
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- WO2009100434A1 WO2009100434A1 PCT/US2009/033561 US2009033561W WO2009100434A1 WO 2009100434 A1 WO2009100434 A1 WO 2009100434A1 US 2009033561 W US2009033561 W US 2009033561W WO 2009100434 A1 WO2009100434 A1 WO 2009100434A1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/52—Propionic acid; Butyric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/90—Ring systems containing bridged rings containing more than four rings
- C07C2603/91—Polycyclopentadienes; Hydrogenated polycyclopentadienes
Definitions
- This invention relates to a process for the conversion of carbohydrates from any of a number of sources into butanol and hexanol for fuel or chemical use.
- the invention uses a combination of homoacetogenic fermentation and acidogenic fermentation to greatly increase the yield of butanol and hexanol from carbohydrates.
- acetone-butanol-ethanol fermentation has been known and practiced industrially for nearly 100 years.
- the biology, history and technology are reviewed in detail by Acetone-Butanol Fermentation Revisited, Microbial Reviews, Dec. 2006; 50(4); 484-524.
- the yield of total solvents, A+B+E, from carbohydrates are reported as about 32 % w/w.
- There are two phases in the fermentation in which first acids are produced and subsequently solvents are produced from the acids. However not all of the acids, mainly acetic acid and butyric acid, are converted to solvents, so the final fermentation broth contains a number of co-products which need to be recovered or treated. Major co- products are also H 2 and CO 2 . All of the biochemical pathways have been studied.
- One method of the present invention is a method to produce butanol and hexanol.
- the method includes conducting a homoacetogenic fermentation in a medium that includes a carbohydrate source to produce acetate, acetic acid or mixtures thereof. A portion of the acetate, acetic acid or mixtures is chemically converted to ethanol.
- An acidogenic fermentation is conducted in a medium that comprises the ethanol and a portion of the acetate, acetic acid or mixtures thereof to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
- the method further includes chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to butanol and hexanol.
- At least about 70%, at least about 80% or at least about 90%, of carbon in the carbohydrate source is converted into butanol and hexanol.
- essentially none of the carbon in the carbohydrate source is evolved as carbon dioxide.
- the chemical energy efficiency of the method can be at least about 50%, at least about 60%, or at least about 70%.
- the yield of butanol and hexanol can be at least about lOOgal/BDT of the carbohydrate source, at least about 120 gal/BDT of the carbohydrate source, or at least about 140 gal/BDT of the carbohydrate source.
- the step of chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol can include acidifying the homoacetogenic fermentation medium to convert acetate to acetic acid, esterifying the acetic acid, and reducing the acetic acid ester to form ethanol.
- the step of acidifying can include introducing carbon dioxide, or an acid with a pKa lower than acetic acid, to the fermentation medium comprising a salt of acetic acid.
- the step of acidifying can comprise introducing an amine with carbon dioxide to the fermentation medium to form an acetic acid/amine complex.
- This embodiment can also include contacting the acid/amine complex with a water immiscible solvent to form an ester of the water immiscible solvent and the acetic acid.
- the step of chemically converting butyrate, butyric acid, caproate, caproic acid or mixtures thereof to butanol and hexanol can include acidifying the acidogenic fermentation medium to convert butyrate and caproate to butyric acid and caproic acid, esterifying the butyric acid and caproic acid, and reducing the butyric acid and caproic acid esters to form butanol and ethanol.
- the step of acidifying can include introducing carbon dioxide, or an acid with a pKa lower than butyric acid and caproic acid, to the fermentation medium comprising a salt of butyric acid and caproic acid.
- the step of acidifying can include introducing an amine with carbon dioxide to the fermentation medium to form butyric acid/amine and caproic acid/amine complexes.
- This embodiment can also include contacting the acid/amine complexes with a water immiscible solvent to form an ester of the water immiscible solvent and the butyric acid and an ester of the water immiscible solvent and the caproic acid.
- the step of reducing can be conducted with a reductant that is produced by thermochemical processing of a portion of a carbon-containing material.
- the thermochemical processing can be selected from gasification, pyrolysis, reforming, and partial oxidation.
- the carbohydrate source for the homoacetogenic fermentation can be derived from a portion of the carbon-containing material.
- the step of reducing can be selected from hydrogenation, hydrogenolysis, and reduction by carbon monoxide.
- the homoacetogenic fermentation of methods of the present invention can include culturing a microorganism of the genus Moorella or Clostridium in a fermentation medium. More particularly, the microorganism can be a microorganism of the species Moorella thermoaceticum or Clostridium formicoaceticum.
- the acidogenic fermentation can include culturing a microorganism of the genus Clostridium in a medium. More particularly, the acidogenic fermentation can include culturing a microorganism of the species Clostridium kluyveri in the medium.
- the carbohydrate source can be derived from a material having carbon-containing compounds that includes carbohydrate substances and non-carbohydrate substances.
- the carbohydrate source can be derived from a material comprising containing carbon-containing compounds by fractionating the material to form a carbohydrate-containing fraction for homoacetogenic fermentation and to form a residue fraction comprising lignin for conversion to a product by a thermochemical conversion process.
- the product of the thermochemical conversion process can be used in the step of chemically converting a portion of the acetate, acetic acid, or mixtures thereof to ethanol or the step of chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to the butanol and hexanol or both.
- the step of fractionating can be selected from 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, or base treatment.
- the material from which the carbohydrate source is derived can include biomass or can be selected from herbaceous matter, agricultural residue, forestry residue, municipal solid waste, waste paper, pulp and paper mill residue. Further, the material can be selected from 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 or soft woods.
- the material can also be selected from trees, grasses, whole plants, and structural components of plants.
- Another method of the present invention produces butanol and hexanol.
- This method includes conducting an acidogenic fermentation in a medium that includes ethanol and acetate, acetic acid or mixtures thereof.
- This acidogenic fermentation produces butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
- the method further includes chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to butanol and hexanol.
- the acetate, acetic acid or mixtures thereof is produced by conducting a homoacetogenic fermentation in a medium that includes a carbohydrate source.
- the ethanol can be produced by conducting a homoacetogenic fermentation in a medium with a carbohydrate source to produce acetate, acetic acid or mixtures thereof and chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol.
- At least about 70%, at least about 80%, or at least about 90% of the carbon in the ethanol and acetate, acetic acid or mixtures thereof is converted into butanol and hexanol.
- essentially none of the carbon in the ethanol and acetate, acetic acid or mixtures thereof is evolved as carbon dioxide
- the chemical energy efficiency of the method can be at least about 50%, at least about 60%, or at least about 70%.
- the yield of butanol and hexanol can be at least about 100 gal/BDT of carbohydrate source, at least about 120 gal/BDT of carbohydrate source, or at least about 140 gal/BDT of carbohydrate source.
- the steps of chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol and of chemically converting butyrate, butyric acid, caproate, caproic acid or mixtures thereof to butanol and hexanol can include the specific chemical converting process steps described above.
- the microorganisms for conducting either a homoacetogenic fermentation or an acidogenic fermentation can be the same as specifically described above.
- the carbohydrate source can be the same as specifically described above.
- Another method of the present invention is a method to produce butanol and hexanol from a material having carbon-containing compounds that includes carbohydrate substances and non-carbohydrate substances.
- This method includes conducting a homoacetogenic fermentation in a medium that includes at least a portion of the carbohydrate substances to produce acetate, acetic acid or mixtures thereof. At least a portion of the non-carbohydrate substances are processed by a thermochemical processing method to produce a reductant. A portion of the acetate, acetic acid or mixtures thereof is chemically converted to ethanol using the reducant. The method further includes conducting an acidogenic fermentation in a medium that includes the ethanol and a portion of the acetate, acetic acid or mixtures thereof to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof, which are chemically converted to the butanol and hexanol using the reductant.
- the step of chemically converting the acetate, acetic acid or mixtures thereof to ethanol can include acidifying the homoacetogenic fermentation medium to convert acetate to acetic acid, esterifying the acetic acid, and reducing the acetic acid ester to form ethanol using the reductant.
- This embodiment also includes the step of chemically converting butyrate, butyric acid, caproate, caproic acid or mixtures thereof to butanol and hexanol by acidifying the acidogenic fermentation medium to convert butyrate and caproate to butyric acid and caproic acid, esterifying the butyric acid and caproic acid, and reducing the butyric acid and caproic acid esters to form butanol and ethanol using the reductant.
- the steps of reducing can be selected from hydrogenation, hydrogenolysis, and reduction by carbon monoxide.
- the thermochemical processing can be selected from gasification, pyrolysis, reforming, and partial oxidation.
- Figure 1 illustrates a specific embodiment of the invention for the production of butanol and hexanol having an acetogenic and an acidogenic fermentation.
- Figure 2 is a comparison of the chemical energy flows and chemical efficiencies of an ABE fermentation process, a butyric acid hybrid process and a process of the invention when using biomass such as wood as the raw material.
- Methods of the present invention are for the production of mixtures of butanol and hexanol with high carbon yield and weight yield as well as high energy efficiency.
- the methods can generally involve the use of a homoacetogenic fermentation and an acidogenic fermentation in which the carbon and weight yields are very high, substantially without the production of carbon dioxide so that substantially all of the carbon substrates in the fermentations are converted to product.
- the methods can generally involve using a portion of the product of the homoacetogenic fermentation, namely acetate, acetic acid or mixtures, for chemical conversion to ethanol which is then used as a substrate in the subsequent acidogenic fermentation.
- a portion of the product of the homoacetogenic fermentation (acetate, acetic acid or mixtures) is also used as a substrate in the subsequent acidogenic fermentation along with the ethanol.
- the acidogenic fermentation produces butyrate, butyric acid, caproate, caproic acid or a mixture which are then chemically converted to butanol and hexanol. Since the methods involve the use of a homoacetogenic and an acidogenic fermentation, higher carbon and weight yield and better energy efficiency are achieved than for other known methods for producing butanol and hexanol. In addition, particularly high carbon and weight yield and improved energy efficiencies can be achieved when all of the fractions of a complex raw material such as biomass are used.
- methods of the present invention can include the use of non-carbohydrate fractions in the various chemical conversion steps to provide significant advantages over alternative processes when using biomass as the feedstock.
- One particular embodiment of the present invention is a method to produce butanol and hexanol. This method includes conducting a homoacetogenic fermentation in a medium containing a carbohydrate source. The homoacetogenic fermentation step of the process produces acetate, acetic acid or mixtures thereof as an acetic acid intermediate. The process further includes chemically converting a portion of the acetate, acetic acid, or mixture into ethanol.
- This embodiment further includes conducting an acidogenic fermentation in a medium that comprises both ethanol that is produced by the chemical conversion of the acetate, acetic acid or mixtures of both and a portion of the acetate, acetic acid, or mixture from the homoacetogenic fermentation that is not chemically converted to ethanol.
- the acidogenic fermentation produces a variety of products including butyrate, butyric acid, caproate, caproic acid or a mixture of all the products.
- This embodiment further includes chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof into butanol and hexanol. Homoacetofienic Fermentation
- a homoacetogenic fermentation refers to culturing a homoacetogenic microorganism to produce acetic acid, acetate or mixtures thereof.
- Homoacetogenic microorganisms are a class of bacteria that utilize a unique biochemical pathway to produce acetic acid from sugars with 100% carbon yield. For example, three moles of glucose can be converted to nine moles of acetic acid by Clostridium thermoaceticum, as shown below: 3 C 6 H 12 O 6 -> 9 CH 3 COOH (1)
- Homoacetogens or homofermentative microorganisms internally convert CO 2 into acetate. They do not convert any of the carbohydrate to CO 2 and only produce acetic acid. Examples of homoactogens are disclosed in Drake, H. L. (editor), Acetogenesis, Chapman & Hall, 1994, which is incorporated herein by reference in its entirety.
- these homofermentative organisms typically convert a wide range of sugars into acetic acid, including glucose, xylose, fructose, lactose, and others. Thus, they are particularly suited to the fermentation of complex hydro lyzates from biomass.
- Suitable microorganisms for conducting a homoacetogenic fermentation include microorganisms of the genera Moorella and Clostridium. Specifically, microorganisms of the species Moorella thermoaceticum (formerly classified as Clostridium thermoaceticum) or Clostridium formicoaceticum are suitable for conducting a homoacetogenic fermentation of the present invention. There are now about one hundred acetogens known in twenty-two genera, with the most studied by far being Moorella thermoacetica (formerly Clostridium thermoaceticum). A current review of acetogens can be found in Drake, et al, Ann. NY Acad. Sci. 1125: 100-128 (2008), which is incorporated herein by reference in its entirety.
- WO 00/53791 describes the use of corn as a raw material for a fermentation substrate, where several pretreatment steps are performed in corn milling, and subsequent processing is conducted for the use of starch, cellulose, hemicellulose, or protein fractions.
- Use of corn fractions as a fermentation substrate can be accomplished by overlapping the saccharification activity with the fermentation process in a design called Simultaneous Saccharification and Fermentation (SSF).
- SSF Simultaneous Saccharification and Fermentation
- a carbohydrate source in a fermentation medium for the homoacetogenic fermentation can be derived from a material comprising carbon- containing compounds that comprise carbohydrate substances and non-carbohydrate substances, and such a material can be biomass.
- the biomass can be selected from herbaceous matter, agricultural residue, forestry residue, municipal solid waste, waste paper, pulp or paper mill residue.
- the material can be selected from 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 or soft woods.
- the material can be selected from trees, grasses, whole plants, or structural components of plants.
- the products are produced from a material comprising carbon- containing compounds, wherein less than about 75% by weight of the carbon-containing compounds are carbohydrate substances.
- the processes of the present invention are particularly suitable for such materials because the non-carbohydrate substances can be used to produce product in part, such as the use of hydrogen from the gasification of a non-carbohydrate substance in a hydrogenation or hydrogenolysis step.
- the carbohydrate source is derived from a material comprising carbon-containing compounds by fractionating the material to form a carbohydrate-containing fraction for homoacetogenic fermentation, and to form a residue fraction comprising lignin for conversion to a product by a thermochemical conversion process.
- the step of fractionating can be selected from 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.
- the product of the thermochemical conversion process can be used in the step of chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol or the step of chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to the butanol and hexanol or both.
- Process conditions, media and equipment suitable for homoacetogenic fermentation of microorganisms of the present invention are known in the art and can be selected based on the microorganism being used.
- the product of the homoacetogenic fermentation step of the process is an acetic acid intermediate that comprises acetate, acetic acid or mixtures thereof.
- the process further includes chemically converting a portion of the acetate, acetic acid, or mixture into ethanol as described below.
- a different portion of the acetate, acetic acid, or mixture, along with the ethanol, is used as a substrate for an acidogenic fermentation, as described below.
- Chemical Conversion of Acetic Acid to Ethanol A portion of the acetic acid intermediate that comprises acetate, acetic acid or mixtures thereof produced by the homoacetogenic fermentation is chemically converted to ethanol.
- the amount of the acetic acid intermediate that is chemically converted to ethanol depends on the relative amounts of ethanol and acetic acid intermediate required by a microorganism in a subsequent acidogenic fermentation.
- the amount of acetic acid intermediate that is converted to ethanol results in sufficient ethanol that, in combination with the remaining acetic acid intermediate, the needs of the microorganism in a subsequent acidogenic fermentation are met without significant excess of either ethanol or acetic acid intermediate.
- a step in the process of chemical conversion can be formation of an ester of acetic acid. Esterification is easy when an organic acid is present in its protonated acid form
- a salt form e.g. calcium acetate
- the acetate salt is preferably converted to the acid, and the acid must be removed from the dilute solution in water.
- the step of acidifying can include introducing carbon dioxide or an acid with a lower pKa than the carboxylic acid being acidified to a solution comprising the salt of the carboxylic acid.
- the step of acidifying includes introducing a tertiary amine with carbon dioxide to form an acid/amine complex.
- carbon dioxide and tributyl amine (TBA) react with calcium acetate to form an amine complex and calcium carbonate:
- This process can further include contacting the acid/amine complex with a water immiscible solvent (e.g., an alcohol capable of forming a separate liquid phase with water (e.g. n-butanol, pentanol, hexanol, octanol, etc.) to form an ester of the water immiscible solvent and the carboxylic acid.
- a water immiscible solvent e.g., an alcohol capable of forming a separate liquid phase with water (e.g. n-butanol, pentanol, hexanol, octanol, etc.
- the organic extract containing the alcohol and the TBA:HAc complex can be heated and the ester formed directly from the complex: Esterification: TBA:HAc + BuOH -> TBA + BuAc + H 2 O (3)
- Water can be distilled from the reaction mass to drive the reaction to completion. After the reaction is complete, the mixture can be distilled to recover the TBA and excess butanol for recycle, and the butyl acetate intermediate can be further processed.
- Other water immiscible alcohols can be used including pentanol, hexanol, etc. Methods of acidification and esterification are described in more detail in PCT
- the ester When an ester is formed in the process of chemical conversion of the acetic acid intermediate to ethanol, the ester can be reduced to form ethanol.
- the ester can be reduced by a process selected from hydrogenation, hydro genolysis or reduction by carbon monoxide.
- Hydrogenolysis refers to simultaneous hydrolysis and hydrogenation.
- An example of reduction by carbon monoxide is U.S. Patent No. 4,851,344 for "Microbial Reduction of Monocarboxylic and Dicarboxylic Acids in the Presence of Carbon Monoxide and/or Formates Plus Mediators".
- the reaction can be catalyzed by any suitable hydrogenation catalysts, such as copper chromite, nickel, Raney nickel, ruthenium, and platinum.
- a copper chromite, nickel, or Raney nickel catalyst is preferred for the hydrogenation since these catalysts are not poisoned by water.
- an alcohol such as ethanol is a good solvent.
- an ester feed in a gas phase process, can be vaporized and fed to a hydrogenation reactor with an excess of hydrogen. After passing through the bed, the vapors are cooled and flashed into a low pressure knockout drum. The hydrogen rich vapor phase is recycled back to the reactor. The product (e.g., ethanol) is separated from unreacted ester and alcohol solvent which can be recycled for further reaction.
- Another refining process such as a distillation column can be used as a final polishing step, depending upon the nature and quantities of side products from the esterification and hydrogenation units.
- Preferred acetate esters for the production of ethanol are butyl acetate or hexyl acetate, as each avoids the introduction of a second compound into the process which must be purified away from the product stream.
- a water stripper can be used to collect water streams from the acidification, esterification, and hydrogenation units.
- the water can be steam stripped to recover solvent values, then the water is sent to final treatment and discharge or recycled to the fermentation section.
- Many potential sources of hydrogen for use in the present invention exist. Any suitable hydrogen source can be used that produces hydrogen of sufficient purity for the hydrogenation reaction and that will not poison the catalyst.
- Raw materials for hydrogen production include water from which hydrogen can be produced by electrolysis.
- Many fossil and renewable organic feedstocks can also be used. If a fossil feedstock is used, such as methane from natural gas, some CO 2 will be produced along with the hydrogen. However, if a renewable feedstock is used then the CO 2 production will be neutral to the environment. For example, almost any feedstock that contains carbon can be used to produce hydrogen.
- Wood chips, sawdust, municipal wastes, recycled paper, wastes from the pulp and paper industry, solid agricultural wastes from animal and/or crop production are all examples of renewable feedstocks that can be used for hydrogen production, e.
- hydrogen can be obtained from a material comprising carbon-containing compounds that comprises carbohydrate substances and non- carbohydrate substances as described in WO 2008/098254 for "Energy Efficient Methods to Produce Products" which is incorporated herein by reference in its entirety.
- thermochemical conversion processes can be used to convert non-carbohydrate substances. Such thermochemical conversion processes can include gasification, pyrolysis, reforming, and partial oxidation. Such processes can produce intermediates that can include hydrogen, carbon monoxide, carbon dioxide, methanol and/or mixtures thereof.
- This embodiment provides the ability to use all of the fractions of a complex raw material such as biomass because while a carbohydrate fraction of a complex raw material is converted by the fermentation step, the non-carbohydrate residue of the complex raw material can be converted to hydrogen for the chemical conversion step. This is a key factor in the advantage of this embodiment over alternative processes when using biomass as the feedstock.
- Methods of the present invention can further include conducting an acidogenic fermentation in a medium comprising the ethanol and a portion of the acetate, acetic acid or mixtures thereof to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
- acidogenic refers to a fermentation process that converts a carbon source to one or more organic acids, without the production of carbon dioxide. Such a process can include the production of other species, such as hydrogen.
- Acidogenic fermentations can be conducted by culturing microorganisms that convert a carbon source to one or more organic acids, without the production of carbon dioxide.
- species of the bacteria Clostridium can convert ethanol and acetic acid to butanol and caproic acid.
- Clostridium kluyveri can convert ethanol and acetic acid essentially to butyric acid, caproic acid and hydrogen in a process under which no CO 2 is produced (see, e.g., Stanier et al, Microbial World, Prentice Hall, 1976; Thauer et al., European J. Biochem., 4 (1968) pp. 173-180, both of which are hereby incorporated by reference in their entirety).
- a strain of Clostridium kluyveri is available from the ATCC as ATCC 8527.
- Process conditions, media and equipment suitable for fermentation of microorganisms of the present inventions are known in the art and can be selected based on the microorganism being used.
- At least about 70 % of carbon in the carbohydrate source is converted into the butanol and hexanol
- at least about 75 % of carbon in the carbohydrate source is converted into the butanol and hexanol
- at least about 80 % of carbon in the carbohydrate source is converted into the butanol and hexanol
- at least about 85 % of carbon in the carbohydrate source is converted into the butanol and hexanol
- at least about 90 % of carbon in the carbohydrate source is converted into the butanol and hexanol
- at least about 95 % of carbon in the carbohydrate source is converted into the butanol and hexanol.
- essentially none of the carbon in the carbohydrate source is evolved as carbon dioxide.
- the chemical energy efficiency of methods of the present invention for producing butanol and hexanol can be very high.
- the chemical energy efficiency of such methods for producing butanol and hexanol from a material comprising carbon- containing compounds, wherein less than about 75% by weight of the carbon-containing compounds are carbohydrate substances can be at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%.
- the present invention can also achieve high yields of butanol and hexanol.
- the yield of butanol and hexanol when being produced from a material comprising carbon-containing compounds, wherein less than about 75% by weight of the carbon-containing compounds are carbohydrate substances can be at least about 100 gal/BDT of carbohydrate source, be at least about 110 gal/BDT of carbohydrate source, be at least about 120 gal/BDT of carbohydrate source, be at least about 130 gal/BDT of carbohydrate source, be at least about 140 gal/BDT of carbohydrate source, be at least about 150 gal/BDT of carbohydrate source.
- a particular embodiment of the present invention is a method to produce butanol and hexanol from a material comprising carbon-containing compounds that comprise carbohydrate substances and non-carbohydrate substances.
- the method includes conducting a homoacetogenic fermentation in a medium comprising at least a portion of the carbohydrate substances to produce acetate, acetic acid or mixtures thereof.
- the method further includes processing at least a portion of the non-carbohydrate substances by thermochemical processing to produce a reductant and chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol using the reductant.
- An acidogenic fermentation is conducted in a medium comprising the ethanol and a portion of the acetate, acetic acid or mixtures thereof to produce butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
- the method then includes chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to the butanol and hexanol using the reductant.
- the step of chemically converting a portion of the acetate, acetic acid or mixtures thereof to ethanol comprises acidifying the homoacetogenic fermentation medium to convert acetate to acetic acid; esterifying the acetic acid; and reducing the acetic acid ester to form ethanol using the reductant.
- Those embodiments also include the step of chemically converting butyrate, butyric acid, caproate, caproic acid or mixtures to butanol and hexanol comprises acidifying the acidogenic fermentation medium to convert butyrate and caproate to butyric acid and caproic acid; esterifying the butyric acid and caproic acid; and reducing the butyric acid and caproic acid esters to form butanol and ethanol using the reductant.
- the steps of reducing can be selected from hydrogenation, hydrogenolysis and reduction by carbon monoxide.
- the thermochemical processing can be selected from gasification, pyrolysis, reforming, and partial oxidation.
- a further embodiment of the present invention is a method to produce butanol and hexanol that includes conducting an acidogenic fermentation.
- the fermentation is conducted in a medium that includes ethanol and acetate, acetic acid or mixtures thereof.
- the fermentation produces butyrate, butyric acid, caproate, caproic acid or mixtures thereof.
- the method further includes chemically converting the butyrate, butyric acid, caproate, caproic acid or mixtures thereof to the butanol and hexanol.
- the ethanol and the acetate, acetic acid or mixtures thereof can be derived from any source.
- the ethanol can be produced by any conventional ethanol production method, such as yeast fermentation of glucose from corn dry milling or wet milling or yeast fermentation from cane sugar juice or molasses.
- the acetate, acetic acid or mixtures thereof can also be produced by any conventional production method, such as the petrochemical route from natural gas, or the vinegar process from ethanol.
- the acetate, acetic acid or mixtures thereof are produced by conducting a homoacetogenic fermentation in a medium that includes a carbohydrate source to produce acetate, acetic acid or mixtures thereof.
- the ethanol is produced by conducting a homoacetogenic fermentation in a medium that includes a carbohydrate source to produce acetate, acetic acid or mixtures thereof a portion of which is then chemically converted to ethanol.
- This method of converting ethanol and acetate, acetic acid or mixtures thereof to butanol and hexanol is highly efficient at converting carbon in a carbohydrate source to butanol and hexanol because of the use of an acidogenic fermentation.
- At least about 70 % of carbon in the carbon source is converted into the butanol and hexanol
- at least about 75 % of carbon source is converted into the butanol and hexanol
- at least about 80 % of carbon source is converted into the butanol and hexanol
- at least about 85 % of carbon source is converted into the butanol and hexanol
- at least about 90 % of carbon source is converted into the butanol and hexanol
- or at least about 95 % of carbon source is converted into the butanol and hexanol.
- essentially none of the carbon in the ethanol and acetate, acetic acid or mixtures thereof is evolved as carbon dioxide.
- a specific embodiment of the present invention is illustrated wherin a biomass feedstock comprising approximately 60 % carbohydrate and 40% residue, which is typical of most biomass such as wood or grasses is converted to butanol and hexanol.
- a biomass 10 is subjected to chemical fractionation 20.
- the biomass 10 can be selected from a wide range of materials as is generally described above.
- One fraction 30 comprises fermentable sugars or materials that can readily be converted to fermentable sugars.
- biomass typically includes a carbohydrate fraction and a non-carbohydrate fraction.
- the carbohydrate fraction can include cellulose, hemicellulose, starch and sugars.
- Cellulose, hemicellulose and starch typically include sugars such as glucose, xylose, arabinose, mannose, etc.
- Another fraction 40 is a non- carbohydrate fraction that can include lignin, which is a complex phenolic material, as well as proteins, resinous materials and minerals.
- the fraction 40 can be put through a gasification process 100 where hydrogen gas 110 is produced.
- the hydrogen gas 110 may either be used in the step of hydrogenation 120 for the purpose of producing ethanol 130, or be utilized in the hydrogenation 210 step to produce butanol and hexanol 220.
- the fraction 30 that comprises fermentable sugars or materials that can readily be converted to fermentable sugars is used as a substrate in an acetogenic fermentation 50.
- the product of the acetogenic fermentation 50 is acetate, acetic acid and mixtures thereof and the fermentation medium comprising these components can be acidified to acetic acid 60.
- the purpose of the fermentation process is to convert fermentable carbohydrates into acetic acid.
- the acetic acid 60 is then directed through an esterification process 70 with an alcohol 90, such as methyl or ethyl alcohol, to form volatile esters 80.
- a reactive distillation process can be used to drive the acidification and esterification processes to a high conversion.
- the conversion of the ester 80 of the acetic acid 60 into two alcohols is achieved by hydrogenation 120 using hydrogen 110 from the gasification process 100.
- hydrogenation 120 uses hydrogen 110 from the gasification process 100.
- the hydrogenation processl20 forms ethanol 130 and another alcohol 90.
- the other alcohol 90 is recycled back to the step of esterification.
- the other alcohol 90 can be any alcohol, including ethanol.
- Fractions of ethanol 130 from hydrogenation 120 and acetic acid 60 from the acetogenic fermentation 50 are combined for use as a substrate in an acidogenic fermentation 150 to produce butyric acid, butyrate, caproic acid, caproate and mixtures thereof and the fermentation medium comprising these components can be acidified to butyric acid and caproic acid 160.
- the butyric and caproic acids 160 are subjected to an esterification process 170 where the acids are converted into esters 180.
- the conversion of the ester 180 of the butyric and caproic acids 160 into alcohols is achieved by hydrogenation 210.
- Hydrogen gas 200 from the gasification process 100 is supplied to the hydrogenation step 210.
- the hydrogenation 210 of the esters 180 of butyric and caproic acids 160 converts the esters into butanol, hexanol, and mixtures thereof 220 and another alcohol 190.
- the other alcohol 190 produced by the hydrogenation process 210 is recycled 190 back to the esterification step 170 of the acid mixture.
- Processes of the present invention provide significantly higher capture of chemical energy flows from biomass to higher alcohol product and higher chemical efficiencies than other known technologies.
- Figure 2 a comparison between two known technologies for producing butanol and an embodiment of the present invention are shown.
- the different paths in Figure 2 show the various process steps in the three different technologies, along with the chemical energy flows, normalized to the starting biomass being equal to 100, shown in bolded and underlined numbers.
- the chemical efficiency for each of the technologies with a yield of 200 gal/BDT (Bone Dry Ton) assumed to be 100% chemical efficiency based on the energy content (HFTV-higher heating value) of wood.
- the ABE Fermentation technology calculations are based on Acetone-Butanol Fermentation Revisited, Microbial Reviews, Dec. 2006; 50(4); 484-524, and the Butyric Acid Hybrid technology calculations are based on US Patent Publication 2008/0248540.
- the Acidogenic Hybrid technology is an embodiment of the present invention. As shown in Figure 2, the chemical energy flow for the ABE Technology results in 30% of the chemical energy of the starting biomass being converted to butanol, ethanol and acetone and the Butyric Acid Hybrid technology results in 50% of the chemical energy of the starting biomass being converted to butanol. In contrast, the Acidogenic Hybrid technology of the present invention results in 75% of the chemical energy of the starting biomass being converted to butanol and hexanol. In addition, the yield for the Acidogenic Hybrid technology of the present invention is 150 gal/BDT, which is significantly higher than the yields of the Butyric Acid Hybrid technology (100 gal/BDT) and the ABE Technology (60 gal/BDT).
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Abstract
Description
Claims
Priority Applications (7)
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BRPI0905949-0A BRPI0905949A2 (en) | 2008-02-07 | 2009-02-09 | Indirect butanol and hexanol production |
CN200980112342XA CN101990576A (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol |
NZ587093A NZ587093A (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol |
EP09709385A EP2252697A4 (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol |
JP2010546092A JP2011511639A (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol |
MX2010008587A MX2010008587A (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol. |
AU2009212131A AU2009212131A1 (en) | 2008-02-07 | 2009-02-09 | Indirect production of butanol and hexanol |
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US2691008P | 2008-02-07 | 2008-02-07 | |
US61/026,910 | 2008-02-07 |
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EP (1) | EP2252697A4 (en) |
JP (1) | JP2011511639A (en) |
CN (1) | CN101990576A (en) |
AU (1) | AU2009212131A1 (en) |
BR (1) | BRPI0905949A2 (en) |
MX (1) | MX2010008587A (en) |
NZ (1) | NZ587093A (en) |
WO (1) | WO2009100434A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4851344A (en) | 1987-02-19 | 1989-07-25 | Basf Aktiengesellschaft | Microbial reduction of monocarboxylic and dicarboxylic acids in the presence of carbon monoxide and/or formates plus mediators |
US5753474A (en) * | 1995-12-26 | 1998-05-19 | Environmental Energy, Inc. | Continuous two stage, dual path anaerobic fermentation of butanol and other organic solvents using two different strains of bacteria |
US6136577A (en) * | 1992-10-30 | 2000-10-24 | Bioengineering Resources, Inc. | Biological production of ethanol from waste gases with Clostridium ljungdahlii |
US6509190B2 (en) | 1997-11-12 | 2003-01-21 | The Trustees Of Columbia University In The City Of New York | DNA regulatory element for the expression of transgenes in neurons of the mouse forebrain |
US20030077771A1 (en) * | 1999-03-11 | 2003-04-24 | Zeachem, Inc. | Process for producing ethanol |
US20080248540A1 (en) | 2007-04-03 | 2008-10-09 | The Ohio State University | Methods of producing butanol |
US8252567B2 (en) | 2008-02-07 | 2012-08-28 | Zeachem, Inc. | Method for the indirect production of butanol and hexanol |
Family Cites Families (70)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US575474A (en) * | 1897-01-19 | To the walmslet | ||
US1421605A (en) | 1921-04-05 | 1922-07-04 | Us Ind Alcohol Co | Process for manufacturing esters |
US2079414A (en) | 1932-08-20 | 1937-05-04 | Du Pont | Process for producing alcohols from esters of nonaromatic carboxylic acids |
US2565487A (en) | 1948-12-27 | 1951-08-28 | Edward M Filachione | Production of esters |
US2782243A (en) | 1954-03-29 | 1957-02-19 | Union Carbide & Carbon Corp | Hydrogenation of esters |
NL243096A (en) | 1958-09-09 | 1900-01-01 | ||
US3769329A (en) | 1970-03-12 | 1973-10-30 | Monsanto Co | Production of carboxylic acids and esters |
IL39710A (en) | 1972-06-19 | 1975-04-25 | Imi Inst For Res & Dev | Recovery of acids from aqueous solutions by solvent extraction |
FR2308611A1 (en) | 1975-04-24 | 1976-11-19 | Rhone Poulenc Ind | PROCESS FOR RECOVERING ACETIC ACID FROM ITS LOW CONCENTRATION AQUEOUS SOLUTIONS |
FR2315498A1 (en) | 1975-06-26 | 1977-01-21 | Roehm Gmbh | PROCESS FOR PREPARING CARBOXYLIC ACID ESTERS FROM CARBOXYLIC ACID AMINES |
US4113662A (en) | 1976-08-05 | 1978-09-12 | Chevron Research Company | Catalyst for ester hydrogenation |
US4282323A (en) | 1979-10-09 | 1981-08-04 | E. I. Du Pont De Nemours And Company | Removal and concentration of lower molecular weight organic acids from dilute solutions |
US4371619A (en) | 1980-06-23 | 1983-02-01 | Union Carbide Corporation | Acetic acid by fermentation |
US4370507A (en) | 1980-09-11 | 1983-01-25 | Ethyl Corporation | Ethanol from methanol and synthesis gas |
DE3101750A1 (en) | 1981-01-21 | 1982-08-26 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF ETHANOL |
US4431838A (en) | 1981-02-09 | 1984-02-14 | National Distillers And Chemical Corporation | Extractive distillation of alcohol-ester mixtures and transesterification |
IT1190783B (en) | 1981-04-29 | 1988-02-24 | Davy Mckee Oil & Chem | PROCESS FOR HYDROGENOLYSIS OF ESTERS OF CARBOXYLIC ACIDS |
US4353784A (en) | 1981-09-21 | 1982-10-12 | Daicel Chemical Industries, Ltd. | Method of recovery of acetic acid |
US4444881A (en) | 1981-10-26 | 1984-04-24 | Cpc International Inc. | Recovery of organic acids from a fermentation broth |
US4405717A (en) | 1981-10-26 | 1983-09-20 | Cpc International Inc. | Recovery of acetic acid from a fermentation broth |
US4568644A (en) | 1981-12-10 | 1986-02-04 | Massachusetts Institute Of Technology | Fermentation method producing ethanol |
EP0104197B1 (en) | 1982-03-26 | 1986-05-28 | DAVY McKEE (LONDON) LIMITED | Process for the production of ethanol |
JPS5929633A (en) | 1982-08-12 | 1984-02-16 | Kuraray Co Ltd | Method for recovering acetic acid from aqueous solution of acetate |
US4421939A (en) | 1982-10-15 | 1983-12-20 | Union Carbide Corporation | Production of ethanol from acetic acid |
US4497967A (en) | 1984-06-15 | 1985-02-05 | The Halcon Sd Group, Inc. | Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen |
US4649112A (en) | 1984-10-11 | 1987-03-10 | Cpc International Inc. | Utilization of xylan and corn fiber for direct fermentation by clostridium acetobutylicum |
US4830963A (en) | 1985-03-20 | 1989-05-16 | Michigan Biotechnology Institute | Production of acetic acid by an improved fermentation process |
PT83746B (en) | 1985-11-15 | 1988-08-17 | Gist Brocades Nv | PROCESS FOR THE PREPARATION OF NEW IMMOBILIZED BIOCATALYZERS AND FOR THE PRODUCTION OF ETHANOL BY FERMENTATION |
DE3618076A1 (en) | 1986-06-02 | 1987-12-03 | Kernforschungsanlage Juelich | METHOD FOR MICROBIAL ANAEROBIC PRODUCTION OF ACETIC ACID |
US5424202A (en) | 1988-08-31 | 1995-06-13 | The University Of Florida | Ethanol production by recombinant hosts |
US4939294A (en) | 1989-05-22 | 1990-07-03 | Eastman Kodak Company | Preparation of ultra high purity methyl acetate |
US5071754A (en) | 1990-01-23 | 1991-12-10 | Battelle Memorial Institute | Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid |
US5210296A (en) | 1990-11-19 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Recovery of lactate esters and lactic acid from fermentation broth |
US5412126A (en) | 1991-04-17 | 1995-05-02 | The Regents Of The University Of California | Carboxylic acid sorption regeneration process |
US5563069A (en) | 1992-04-24 | 1996-10-08 | The Ohio State University Research Foundation | Extractive fermentation using convoluted fibrous bed bioreactor |
US5865898A (en) | 1992-08-06 | 1999-02-02 | The Texas A&M University System | Methods of biomass pretreatment |
US5693296A (en) | 1992-08-06 | 1997-12-02 | The Texas A&M University System | Calcium hydroxide pretreatment of biomass |
US5562777A (en) | 1993-03-26 | 1996-10-08 | Arkenol, Inc. | Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials |
DE4402694A1 (en) | 1993-06-02 | 1995-08-03 | Hoechst Ag | Process for the recovery of fluorinated carboxylic acids |
IL109724A (en) | 1994-05-23 | 1999-11-30 | Innova Sa | Recovery of carboxylic acid from organic solution that contains an amine and an extraction enhancer |
IL110206A (en) | 1994-07-04 | 1996-10-16 | Innova Sa | Recovery of carboxylic acid from organic solution that contains an amine and an extraction enhancer |
GB9419001D0 (en) | 1994-09-21 | 1994-11-09 | Applied Research Systems | Assay method |
JP2942710B2 (en) * | 1994-11-14 | 1999-08-30 | 昭和電工株式会社 | Water-soluble self-doping type conductive polymer composite and method for producing the same |
US5599976A (en) | 1995-04-07 | 1997-02-04 | Hoechst Celanese Corporation | Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process |
US5723639A (en) | 1995-10-16 | 1998-03-03 | University Of Chicago | Esterification of fermentation-derived acids via pervaporation |
US5874263A (en) | 1996-07-31 | 1999-02-23 | The Texas A&M University System | Method and apparatus for producing organic acids |
US6160173A (en) | 1996-10-09 | 2000-12-12 | Cargill Incorporated | Process for the recovery of lactic acid esters and amides from aqueous solutions of lactic acid and/or salts thereof |
US5766439A (en) | 1996-10-10 | 1998-06-16 | A. E. Staley Manufacturing Co. | Production and recovery of organic acids |
US6043392A (en) | 1997-06-30 | 2000-03-28 | Texas A&M University System | Method for conversion of biomass to chemicals and fuels |
US5986133A (en) | 1997-06-30 | 1999-11-16 | The Texas A&M University System | Recovery of fermentation salts from dilute aqueous solutions |
EP1059975A4 (en) | 1998-03-02 | 2003-04-23 | Michigan Biotech Inst | Purification of organic acids using anion exchange chromatography |
UA72220C2 (en) | 1998-09-08 | 2005-02-15 | Байоенджініерінг Рісорсиз, Інк. | Water-immiscible mixture solvent/cosolvent for extracting acetic acid, a method for producing acetic acid (variants), a method for anaerobic microbial fermentation for obtaining acetic acid (variants), modified solvent and a method for obtaining thereof |
US6703227B2 (en) | 1999-02-11 | 2004-03-09 | Renessen Llc | Method for producing fermentation-based products from high oil corn |
US6740508B2 (en) | 1999-02-11 | 2004-05-25 | Renessen Llc | Fermentation-based products from corn and method |
US7074603B2 (en) | 1999-03-11 | 2006-07-11 | Zeachem, Inc. | Process for producing ethanol from corn dry milling |
US6573409B1 (en) * | 1999-07-02 | 2003-06-03 | The Nutrasweet Company | Process for the preparation of 3,3-dimethylbutanal |
US6926810B2 (en) | 2001-03-15 | 2005-08-09 | A. E. Staley Manufacturing Co. | Process for obtaining an organic acid from an organic acid ammonium salt, an organic acid amide, or an alkylamine organic acid complex |
US20060222585A1 (en) | 2003-01-10 | 2006-10-05 | Zeachem, Inc. | Production of organic acid and ammonium nitrate |
SE526429C2 (en) | 2003-10-24 | 2005-09-13 | Swedish Biofuels Ab | Intensifying fermentation of carbohydrate substrate for, e.g. producing one to five carbon alcohols, involves using amino acid leucine, isoleucine, and/or valine as source of nitrogen |
JP5013879B2 (en) | 2004-01-29 | 2012-08-29 | ズィーケム インコーポレイテッド | Organic acid recovery |
EP2261365A3 (en) | 2004-06-16 | 2012-02-29 | The Texas A&M University System | Methods and systems for biomass conversion to carboxylic acids and alcohols |
US20070014895A1 (en) | 2005-07-12 | 2007-01-18 | Holtzapple Mark T | System and Method for Converting Biomass |
US7309602B2 (en) * | 2006-04-13 | 2007-12-18 | Ambrozea, Inc. | Compositions and methods for producing fermentation products and residuals |
US7670813B2 (en) | 2006-10-25 | 2010-03-02 | Iogen Energy Corporation | Inorganic salt recovery during processing of lignocellulosic feedstocks |
CN101611147A (en) | 2006-12-01 | 2009-12-23 | 得克萨斯A&M大学系统 | Wood Adhesives from Biomass is become the method for alcohol mixture |
EP2121946A4 (en) | 2007-02-09 | 2012-08-29 | Zeachem Inc | Energy efficient methods to procuce products |
US20080280338A1 (en) | 2007-05-11 | 2008-11-13 | Hall Kenneth R | Biofuel Processing System |
CA2692732A1 (en) | 2007-07-27 | 2009-02-05 | Mark T. Holtzapple | Short-flux path motors / generators |
BRPI0908303A2 (en) | 2008-05-07 | 2015-08-18 | Zeachem Inc | Organic Acid Recovery |
US20100120104A1 (en) * | 2008-11-06 | 2010-05-13 | John Stuart Reed | Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products |
-
2009
- 2009-02-09 MX MX2010008587A patent/MX2010008587A/en not_active Application Discontinuation
- 2009-02-09 WO PCT/US2009/033561 patent/WO2009100434A1/en active Application Filing
- 2009-02-09 EP EP09709385A patent/EP2252697A4/en not_active Withdrawn
- 2009-02-09 BR BRPI0905949-0A patent/BRPI0905949A2/en not_active IP Right Cessation
- 2009-02-09 AU AU2009212131A patent/AU2009212131A1/en not_active Abandoned
- 2009-02-09 NZ NZ587093A patent/NZ587093A/en not_active IP Right Cessation
- 2009-02-09 US US12/368,040 patent/US8252567B2/en not_active Expired - Fee Related
- 2009-02-09 CN CN200980112342XA patent/CN101990576A/en active Pending
- 2009-02-09 JP JP2010546092A patent/JP2011511639A/en active Pending
-
2012
- 2012-07-24 US US13/557,024 patent/US20120322118A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4851344A (en) | 1987-02-19 | 1989-07-25 | Basf Aktiengesellschaft | Microbial reduction of monocarboxylic and dicarboxylic acids in the presence of carbon monoxide and/or formates plus mediators |
US6136577A (en) * | 1992-10-30 | 2000-10-24 | Bioengineering Resources, Inc. | Biological production of ethanol from waste gases with Clostridium ljungdahlii |
US5753474A (en) * | 1995-12-26 | 1998-05-19 | Environmental Energy, Inc. | Continuous two stage, dual path anaerobic fermentation of butanol and other organic solvents using two different strains of bacteria |
US6509190B2 (en) | 1997-11-12 | 2003-01-21 | The Trustees Of Columbia University In The City Of New York | DNA regulatory element for the expression of transgenes in neurons of the mouse forebrain |
US20030077771A1 (en) * | 1999-03-11 | 2003-04-24 | Zeachem, Inc. | Process for producing ethanol |
US20080248540A1 (en) | 2007-04-03 | 2008-10-09 | The Ohio State University | Methods of producing butanol |
US8252567B2 (en) | 2008-02-07 | 2012-08-28 | Zeachem, Inc. | Method for the indirect production of butanol and hexanol |
Non-Patent Citations (3)
Title |
---|
FERMENTATION REVISITED, MICROBIAL REVIEWS, vol. 50, no. 4, December 2006 (2006-12-01), pages 484 - 524 |
MICROBIAL REVIEWS, vol. 50, no. 4, December 2006 (2006-12-01), pages 484 - 524 |
See also references of EP2252697A4 * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2121946A2 (en) * | 2007-02-09 | 2009-11-25 | Zeachem, Inc. | Energy efficient methods to procuce products |
EP2121946A4 (en) * | 2007-02-09 | 2012-08-29 | Zeachem Inc | Energy efficient methods to procuce products |
US9175315B2 (en) | 2010-06-18 | 2015-11-03 | Butamax Advanced Biofuels Llc | Production of alcohol esters and in situ product removal during alcohol fermentation |
US9040263B2 (en) | 2010-07-28 | 2015-05-26 | Butamax Advanced Biofuels Llc | Production of alcohol esters and in situ product removal during alcohol fermentation |
CN101948737A (en) * | 2010-08-31 | 2011-01-19 | 天津理工大学 | Acetone-butanol in-situ extraction continuous fermentation device and technology |
CN101948737B (en) * | 2010-08-31 | 2013-06-05 | 天津理工大学 | Acetone-butanol in-situ extraction continuous fermentation device and technology |
US10329590B2 (en) | 2014-05-13 | 2019-06-25 | Evonik Degussa Gmbh | Method of producing nylon |
EP3050968A1 (en) | 2015-01-28 | 2016-08-03 | Evonik Degussa GmbH | An aerobic method of producing alcohols |
EP3050969A1 (en) | 2015-01-28 | 2016-08-03 | Evonik Degussa GmbH | A method of producing higher alcohols |
EP3050967A1 (en) | 2015-01-28 | 2016-08-03 | Evonik Degussa GmbH | A method of producing higher alcohols |
EP3050966A1 (en) | 2015-01-28 | 2016-08-03 | Evonik Degussa GmbH | An aerobic method of producing alcohols |
US10787685B2 (en) | 2015-01-28 | 2020-09-29 | Evonik Operations Gmbh | Method of producing higher alcohols |
US11174496B2 (en) | 2015-12-17 | 2021-11-16 | Evonik Operations Gmbh | Genetically modified acetogenic cell |
CN105567614A (en) * | 2016-03-10 | 2016-05-11 | 安徽金种子酒业股份有限公司 | Fermented pit mud-maintained fungicide and preparation method thereof |
CN105567613A (en) * | 2016-03-10 | 2016-05-11 | 安徽大学 | Method for preparing manmade pit mud |
US11124813B2 (en) | 2016-07-27 | 2021-09-21 | Evonik Operations Gmbh | N-acetyl homoserine |
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CN101990576A (en) | 2011-03-23 |
US20120322118A1 (en) | 2012-12-20 |
BRPI0905949A2 (en) | 2015-06-30 |
JP2011511639A (en) | 2011-04-14 |
AU2009212131A1 (en) | 2009-08-13 |
US8252567B2 (en) | 2012-08-28 |
EP2252697A4 (en) | 2012-05-30 |
NZ587093A (en) | 2012-03-30 |
US20090203098A1 (en) | 2009-08-13 |
MX2010008587A (en) | 2010-09-28 |
EP2252697A1 (en) | 2010-11-24 |
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