WO2010024714A2 - Procédé de production de solvants organiques - Google Patents

Procédé de production de solvants organiques Download PDF

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Publication number
WO2010024714A2
WO2010024714A2 PCT/RU2009/000326 RU2009000326W WO2010024714A2 WO 2010024714 A2 WO2010024714 A2 WO 2010024714A2 RU 2009000326 W RU2009000326 W RU 2009000326W WO 2010024714 A2 WO2010024714 A2 WO 2010024714A2
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WO
WIPO (PCT)
Prior art keywords
butanol
fermentation
fermentor
organic solvents
ethanol
Prior art date
Application number
PCT/RU2009/000326
Other languages
English (en)
Other versions
WO2010024714A3 (fr
Inventor
Evgeniy Rubenovich Davidov
Petr Sergeevich Kanygin
Igor Vladimirovich Cheremnov
Oleg Anatolievich Frakin
Kirill Borisovich Filippov
Original Assignee
Open Joint Stock Company "Corporation Biotechnologies"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Open Joint Stock Company "Corporation Biotechnologies" filed Critical Open Joint Stock Company "Corporation Biotechnologies"
Publication of WO2010024714A2 publication Critical patent/WO2010024714A2/fr
Publication of WO2010024714A3 publication Critical patent/WO2010024714A3/fr

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Classifications

    • 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
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/065—Ethanol, i.e. non-beverage with microorganisms other than yeasts
    • 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
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/16—Butanols
    • 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
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones
    • C12P7/28—Acetone-containing products
    • C12P7/36—Acetone-containing products produced from substrate containing grain or cereal material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a process for production of organic solvents, particularly acetone, butanol, ethanol using the anaerobic fermentation by butanol, acetone, and ethanol- producing bacteria.
  • Butanol is an important industrial chemical and is currently used as solvent in making nitro dopes, synthetic resins; as a feedstock chemical in the plastics industry and as a food grade extractant in the food and pharmaceutical industry.
  • the recent trend of using butanol as biofuel has revived research efforts aimed at obtaining liquid fuels from renewable resources.
  • Butanol is a chemical that has excellent fuel characteristics. It contains approximately 22% oxygen, which used as a fuel extender will result in more complete fuel combustion.
  • Use of butanol as fuel will contribute to clean air by reducing smog-creation compounds, harmful emissions (carbon monoxide).
  • butanol is more miscible with gasoline and diesel fuel, has a lower vapor pressure, and is less miscible with water, qualities that make butanol a superior fuel extender than ethanol.
  • butanol is produced chemically by either the oxo process starting from propylene (with H 2 and CO over rhodium catalyst or nickel-cobalt catalyst) or the aldol process starting from acetaldehyde (Alcoholic fuels, edited by Shelley D. Minteer, CRC Press, 2006, p.100).
  • acetone/butanol/ethanol (ABE) fermentation process has received considerable attention in recent years as a prospective process for the production of butanol and acetone from biomass but in order to make butanol fermentation an economically viable option, a number of problems must be addressed.
  • the first of these relates to low process productivity.
  • SU 1604852 discloses a method for anaerobic fermentation of starch based feedstock by Clostridium acetobutylicum wherein, the fermentation broth containing the amylolytic enzymes was taken off in 24 hours of fermentation process and the starch based feedstock was liquefied with this broth at 70-75 0 C for 15-20 minutes.
  • RU 2044773 discloses a method for fermentation of carbohydrate-containing medium with bacteria which produce butanol, acetone, ethanol and/or isopropanol. The method is carried out in two steps. The first step involves growth of bacteria, at the second step bacteria are immobilized on porous carrier. Products are recovered by extraction with higher alcohols or higher fatty acids or by diffuse evaporation through membrane.
  • US 5753474 describes a process for the manufacture of butanol and like volatile organic compounds by fermenting carbohydrates, mainly polysaccharide, with microorganisms which convert carbohydrates into mainly butyric acid and other acids.
  • the acids are subsequently transferred to solventogenesis production stage using a different strain of bacteria which continuously produces butanol via multistage fermentation process that is stable, high yielding (weight product per unit weight carbohydrate) and productive (faster throughput).
  • the invention is a continuous process for preparing solvents by digesting carbohydrates in the anaerobic fermentation of carbohydrate slurry.
  • the major portion of the carbohydrate slurry and a first acid-producing bacteria are fed into an acid reactor.
  • the continuous fermentation of the carbohydrate in the acid reactor as a result of the activity of the first bacteria forms a solution which includes a short chain organic acid, such as butyric acid.
  • a minor portion of the carbohydrate slurry and a second solvent producing bacteria are fed into a breeder reactor to breed the second bacteria in an acidogenesis phase.
  • the acid solution is extracted from the acid reactor and transferred to a solventogenesis reactor.
  • the acidogenesis bacteria from the breeder reactor are transferred to the solventogenesis reactor.
  • the anaerobic fermentation of the extracted acid as a result of the activity of the second bacteria forms a solution including a short chain alcohol, such as butanol.
  • the alcohol solution is extracted from the solventogenesis reactor at a rate sufficient to maintain the solventogenesis fermentation.
  • the alcohol is separated from the solution.
  • ABE process Another problem of ABE process relates to product toxicity. Many studies today are focused on overcoming the butanol toxicity by developing a more butanol tolerant microorganism.
  • US 5192673 discloses a fermentation process for producing butanol using a mutant strain of Clostridium acetobutylicum designated Clostridium acetobutylicum ATCC 55025.
  • the biologically pure asporogenic mutant of Clostridium acetobutylicum is produced by growing sporogenic Clostridium acetobutylicum ATCC 4259 and treating the parent strain with ethane methane sulfonate.
  • EP 0973929 discloses the fermentation process for producing butanol, acetone and ethanol comprising steps of anaerobically culturing a culture of Clostridium beijerinckii BAlOl in a nutrient medium with assimilable carbohydrates and recovering butanol, acetone and ethanol, the amount of butanol recovered is from about 18 g/1 to about 21 g/1.
  • US 2005089979 discloses a continuous process for production of solvents, particularly acetone-butanol-ethanol using fermentation of solventogenic microorganisms and gas stripping is provided.
  • gas stripping involves passing a flow of stripping gas through a liquid to form a stripping gas enriched in one or ore of the volatile components from the liquid. The volatile components are then removed using means known in the art, for example condensation.
  • US 5755967 discloses a pervaporation process for the selective removal of acetone and/or butanol from Clostridium acetobutylicum fermentation media through silicalite, silicalite filled polymer membrane.
  • the object of the invention is to provide a process which increases the fermentation rate, in higher productivity, a process which requires less energy consumption through providing the optimum conditions for fermentation.
  • a process for production of organic solvents comprising pretreatment of carbohydrate based feedstock, its fermentation by butanol, acetone, ethanol producing bacteria in a fermentor at a nutrient medium, removal of organic solvents and fermentation gases, feeding of carbohydrate and mineral salts solution, wherein the process is carried out with periodic pressure reduction in the fermentor for the fermentation and simultaneous removal of organic solvents and fermentation gases.
  • Butanol, acetone, ethanol producing bacteria includes species of Clostridium, including Clostridium beijerinckii and Clostridium acetobutylicum, as well as another bacteria known in the art.
  • the bacteria are inoculated in a nutrient medium, containing carbohydrate based feedstock and other additives, such as mineral salts.
  • carbohydrate based feedstock examples include sugars such as glucose, mannose, xylose, galactose, fermentolysate of non-food plant polysaccharides, containing glucose, mannose, xylose, arabinose separated from the lignin residues, lactose of cheese whey, etc.
  • Some substrates may require processing prior to fermentation (pretreatment), such as dilution, concentration, filtration, hydrolysis, etc.
  • FIG. 1 shows the concentration of ABE during traditional ABE fermentation.
  • FIG. 2 shows the concentration of ABE during ABE fermentation with solvent removal under periodic pressure reduction.
  • Fermentation processes for ethanol production using yeasts wherein the process runs continuously with simultaneous recovery of ethanol vapor and CO 2 at a reduced pressure are known in the art, see, e.g. US 4359533; GB 2438617; RU 2230788, etc.
  • the headspace pressure in fermentor is reducing to level for providing evaporation, removing and condensation of the ABE vapors.
  • the ABE vapors pressure is reducing and the rate of evaporation is accelerated proportionally degree of pressure reduction.
  • removal of solvent vapors and fermentation gases from headspace leads to accelerated removal from the fermentor.
  • the additional intensification of this process was caused by numerous gas bubbles (CO 2 , H 2 ), which form during biosynthesis and rise to the surface that increase substantially the liquid/gas interface where the organic solvents molecules are accumulated due to surface sorption.
  • the removed gases are directed into cooling device wherein the solvents are condensed and collected in the accumulator tank. Removal of organic solvents maintains until butanol concentration in the fermentation broth will not decrease to the values so as not affect the rate of fermentation, but sufficient to maintain a low level of extraneous microflora. Then removal of the ABE vapors temporarily stops, and nutrients were added into the fermentor to compensate for nutrients loss due to their consumption by producing microorganisms during the previous period. The fermentation is allowed to proceed, butanol concentration begins to rise and a cycle repeats. Feeding of required nutrients can be carried out continuously.
  • Frequency of repetition of cycles depends on the upper (at which start to reduce pressure) and bottom (at which stop removal) butanol concentration in the fermentation broth, on rate of removal of vaporous products, the evaporation area. Varying these parameters, it is possible to increase butanol ratio to 70-90% in comparison with 60 % in known processes. For example, the evaporation area can be increased, providing increase of intensity of "cold" boiling at reduced pressure, the medium spraying by special devices.
  • the standard mixture of carbohydrate and minerals (mineral salts, vitamin and one of the following carbon sources: glucose, mannose, xylose, galactose, fermentolysate of non-food plant polysaccharides, containing glucose, mannose, xylose, arabinose separated from the lignin residues, lactose of cheese whey in concentration of 2-4%) was added into a fe ⁇ nentor. Then the medium was inoculated with cells of Clostridium acetobutylicum VKM B- 1787 with density of 1-2 milliard/ml.
  • a four-liter fe ⁇ nentor containing 2.5 1 of 4% glucose solution, 120 g of flour was inoculated with 300 ml of inoculum of Clostridium acetobutylicum VKPM B-4786 with density of 1-2 milliard/ml, water and flour (40 g/1).
  • the fermentation was allowed to proceed in the batch mode for 72 h.
  • the temperature was maintained at 37 0 C. hi 72 hours the pressure in the fermentor was reduced to - 0.94 kg/cm 2 for 3 hours and the vapors were taken off.
  • the ABE vapors were cooled in a condenser and in result 250 ml of solution, containing 5% butanol, 1.5% acetone and 0.5% ethanol was obtained.
  • Productivity was 3 g/l/day.
  • the ABE vapors were cooled in a condenser and in result 250 ml of solution, containing 6.5% butanol, 2% acetone and 0.75% ethanol was obtained. The procedure of pressure reduction was repeated every time when the butanol concentration approached 9 g/1. After the ABE vapors and fermentation gases removal the nutrient medium containing 50 g/1 of glucose was added into the fermentor. One time in three days 28 g of yeast autolyzate was added into the fermentor. Productivity was 8.5 g/l/day.
  • the upper layer (5-10 ml) contains 70-75% butanol, 2-4% acetone and 0.1- 1% ethanol. As butanol solubility in water is 6.7%, it gives option to separate butanol by decantation.
  • the lower layer contains 5-7% butanol, 0.5-1.5% acetone and 0.1-1% ethanol. As soon as butanol concentration approached 5 g/1, the pressure was gradually increased to atmospheric. The procedure of pressure reduction was repeated every time when the butanol concentration approached 9 g/1. After the ABE vapors and fermentation gases removal the nutrient medium containing 50 g/1 of glucose was added into the fermentor. One time in three days 28 g of yeast autolyzate was added into the fermentor. Productivity was 10 g/l/day.
  • the present improved process gives the possibility to increase productivity, the process requires less energy consumption through providing the optimum conditions for fermentation.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention concerne un procédé de production de solvants organiques, en particulier l'acétone, le butanol, l'éthanol en utilisant la fermentation anaérobie par des bactéries productrices de butanol, d'acétone, et d'éthanol. Le procédé est effectué avec une réduction périodique de la pression dans le fermenteur pour fermenter et éliminer simultanément des solvants organiques et des gaz de fermentation.
PCT/RU2009/000326 2008-08-28 2009-07-01 Procédé de production de solvants organiques WO2010024714A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2008134865/13A RU2375454C1 (ru) 2008-08-28 2008-08-28 Способ получения органических растворителей, преимущественно бутанола
RU2008134865 2008-08-28

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WO2010024714A2 true WO2010024714A2 (fr) 2010-03-04
WO2010024714A3 WO2010024714A3 (fr) 2010-08-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010095975A3 (fr) * 2009-02-18 2011-01-13 Limited Liability Company "Prof Business" Procédé de régulation du rapport de solvants organiques pendant une biosynthèse
EP2398906A1 (fr) * 2009-02-23 2011-12-28 Eugene T. Butler, III Synthèse de butanol par fermentation en continu dans un seul réacteur
US8574406B2 (en) 2010-02-09 2013-11-05 Butamax Advanced Biofuels Llc Process to remove product alcohol from a fermentation by vaporization under vacuum
US8628643B2 (en) 2010-09-02 2014-01-14 Butamax Advanced Biofuels Llc Process to remove product alcohol from a fermentation by vaporization under vacuum
US9962623B2 (en) 2011-12-09 2018-05-08 Butamax Advanced Biofuels Llc Process to remove product alcohols from fermentation broth

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63254986A (ja) * 1987-04-10 1988-10-21 Res Assoc Petroleum Alternat Dev<Rapad> アルコ−ルの製造法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BALLONGUE, J. ET AL.: "Enhancement of Solvents Production by Clostridium acetobutylicum Cultivated on a Reducing Compounds Depletive Medium" BIOMASS, vol. 10, no. 2, 1986, pages 121-129, XP002588300 *
DATABASE WPI Week 198848 Thomson Scientific, London, GB; AN 1988-342292 XP002588301 & JP 63 254986 A (SHINNENRYOYU KAIHAT) 21 October 1988 (1988-10-21) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010095975A3 (fr) * 2009-02-18 2011-01-13 Limited Liability Company "Prof Business" Procédé de régulation du rapport de solvants organiques pendant une biosynthèse
EP2398906A1 (fr) * 2009-02-23 2011-12-28 Eugene T. Butler, III Synthèse de butanol par fermentation en continu dans un seul réacteur
EP2398906A4 (fr) * 2009-02-23 2013-11-06 Eugene T Butler Iii Synthèse de butanol par fermentation en continu dans un seul réacteur
US8574406B2 (en) 2010-02-09 2013-11-05 Butamax Advanced Biofuels Llc Process to remove product alcohol from a fermentation by vaporization under vacuum
US8628643B2 (en) 2010-09-02 2014-01-14 Butamax Advanced Biofuels Llc Process to remove product alcohol from a fermentation by vaporization under vacuum
US9962623B2 (en) 2011-12-09 2018-05-08 Butamax Advanced Biofuels Llc Process to remove product alcohols from fermentation broth

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WO2010024714A3 (fr) 2010-08-26
RU2375454C1 (ru) 2009-12-10

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