WO2010000649A1 - Method for the combined production of butanol and hydrogen - Google Patents
Method for the combined production of butanol and hydrogen Download PDFInfo
- Publication number
- WO2010000649A1 WO2010000649A1 PCT/EP2009/057802 EP2009057802W WO2010000649A1 WO 2010000649 A1 WO2010000649 A1 WO 2010000649A1 EP 2009057802 W EP2009057802 W EP 2009057802W WO 2010000649 A1 WO2010000649 A1 WO 2010000649A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- butanol
- hydrogen
- effluent
- ethanol
- abe
- Prior art date
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Classifications
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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
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- 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
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- the present invention relates to a method for the combined production of butanol, in particular acetone- butanol-ethanol (ABE), and hydrogen from biomass.
- butanol in particular acetone- butanol-ethanol (ABE), and hydrogen from biomass.
- ABE acetone- butanol-ethanol
- Biofuels are renewable fuels made from plant matter rather than fossil fuels.
- Today's primary liquid biofuels are ethanol and biodiesel.
- Other potential biofuels are butanol and hydrogen.
- Butanol is a biofuel which has superior properties with respect to bioethanol. Firstly, butanol producing, or solventogenic, bacteria ensure the conversion of hexoses as well as pentoses in contrast to the ethanol producing yeasts which only utilise hexoses. This way the full utilisation of second generation biomass comes within reach.
- butanol can be applied as a fuel extender in the growing market of diesel engines, in contrast to ethanol which can be used in gasoline engines only.
- butanol can be used to prevent evaporation of ethanol in ethanol- gasoline mixtures.
- butanol is an interesting building block in the chemical industry.
- Hydrogen is the fuel of the future where fuel cells will replace combustion engines due to inter alia the superior energy conversion efficiency. As with butanol, hydrogen is an important commodity in the chemical industry. Hydrogen is produced by many facultative and obligate anaerobic bacteria at various temperatures .
- thermochemical processes are adequate for biomass with low water content ⁇ 20%) and high lignin content and biological (anaerobic ! ) processes are best suited for wet biomass and biomass with high carbohydrate content.
- ABE fermentation is a process that utilizes bacterial fermentation to produce acetone, butanol, ethanol and, to a lesser extent, iso-propanol and hydrogen from a carbohydrate containing substrate.
- ABE fermentation used in the following, stems from the past, where the emphasis was on ABE production. The process is anaerobic. It usually uses saccharolytic solventogenic Clostridia.
- Clostridia produce acetone, butanol and ethanol from carbohydrates, i.e. starch, glucose, xylose and other (oligo) saccharides .
- Other products are hydrogen, CO 2 , iso-propanol and butyric acid.
- Butanol is the product with the highest value and much of the current research is devoted to optimise the ABE fermentation towards butanol production.
- butanol is mainly regarded as a biofuel to be added, after derivatisation, to diesel. Additionally, butanol can be added to gasoline-ethanol mixtures to prevent evaporation of ethanol .
- acetone-butanol-ethanol (ABE) fermentation the process is characterized by two phases.
- the first known as the acidogenic phase
- saccharides are converted to acetic and butyric acids and hydrogen accompanied by a decrease in culture pH value.
- the solventogenic phase sugars and some of the acids are converted to acetone, butanol and ethanol, accompanied by a pH increase.
- Typical concentrations after batch fermentation are 15-19 g/L butanol, 4-6 g/L acetone and ⁇ 1 g/L ethanol.
- Butanol is however toxic and bacteria are killed at concentrations above 20-25 g/L butanol.
- a typical problem that may occur in a batch process is known as the u acid crash" .
- the substrate concentration is usually around 6-8% (w/v) carbohydrate. This relatively high substrate concentration is also necessary to force Clostridia to ABE production during continuous fermentation.
- the amount of H 2 is typically around 100 and 200 Nm 3 per 1000 kg carbohydrate.
- the production of H 2 is in competition with the production of butanol, i.e. more hydrogen means less butanol.
- micro-organisms are able to produce hydrogen from mono- and oligosaccharides, starch and (hemi) cellulose under anaerobic conditions.
- the anaerobic production of hydrogen is a common phenomenon, occurring during the process of anaerobic digestion.
- hydrogen producing micro-organisms are in syntrophy with methanogenic bacteria which consume the hydrogen as soon as it is produced. In this way, hydrogen does not accumulate and methane is the end-product. By uncoupling hydrogen production from methane production, hydrogen becomes available for recovery and exploitation.
- thermophilic bacteria show fairly low yields of hydrogen due to the fact that these bacteria may have metabolic pathways with other, competing reduced end products (e.g. butanol or ethanol) .
- Thermophilic bacteria show yields which can be almost twice as high (e.g. >300 Nm 3 per 1000 kg carbohydrate) , especially when acetic acid is J:he only other end product.
- the optimal substrate concentration in batch fermentation for high hydrogen yield and productivity is relatively low.
- the invention thus relates to a process for the combined production of butanol and hydrogen from biomass, comprising the steps of: a) fermenting biomass to obtain butanol in a first reaction mixture; b) removing the butanol and hydrogen from the first reaction mixture to obtain effluent; and c) using the effluent as a substrate in a second reaction mixture in a process .using low substrate concentrations, in particular a hydrogen production process.
- the butanol may be obtained in an ABE process, wherein it is produced in combination with acetone and ethanol.
- the butanol may be the main or only product of the fermentation process of step a when process parameters are used that force the production in the direction of butanol or when micro-organisms are used that produce only or mainly butanol.
- the second process can be any fermentation process that uses low concentrations of sugars .
- This process uses the residual sugars from the first fermentation.
- the ⁇ process is a hydrogen fermentation in which hydrogen is produced from the sugars in the effluent of the first process.
- Other products that can be produced from the residual sugars are acetate, lactate, pyruvate, butyrate, succinate, formate and/or ethanol. These products may be a by-product of the hydrogen production process or can be the main product of the second process.
- the end products from the second process are removed from the second reaction mixture to obtain an effluent that is returned to the first reaction mixture.
- the metabolites e.g. acetic acid or butyric acid
- the metabolites in the effluent can be recovered, e.g. in the case of ethanol.
- the process of the invention thus starts with butanol production, for example by ABE fermentation of carbohydrates in the biomass.
- the products thus obtained are removed from the effluent and the effluent- is subsequently inoculated with different bacteria for hydrogen production.
- the effluent leaving the hydrogen ferment ⁇ r is preferably recycled to the ABE fermentor.
- Clostridia that are used in the ABE process are saccharolytic solventogenic Clostridium species, for example selected from but not limited to the group consisting of Clostridium acetobutylicum, Clostridium beijerinckii, Clostridium saccharobutylicum and Clostridium butylicum.
- Many strains are commercially available ⁇ for example from DSM or from the ATCC) , or are selected from own culture collections or can be produced by enrichments.
- new ABE producing micro-organisms J.i ⁇ cluding genetically modified micro-organisms, can be used.
- micro-organisms that are used in the second process, in particular for hydrogen production are preferably mesophilic, thermophilic, extreme thermophilic or hyperthermophilic anaerobic hydrogen producing species.
- Such micro-organisms may be selected from but are not limited to Caldicellulosiruptor saccharolyticus, Caldicellulosiruptor owensensis, Caldicellulosiruptor Kristjanssohnii, Thermotoga elfii, Thermotoga neapolitana, Thermotoga maritima and Clostridium thermocellum.
- the advantages of the combined process are many.
- the residual carbohydrate of the ABE fermentation is converted to useful products such as hydrogen, acetate, lactate, pyruvate, butyrate, succinate, formate and ethanol in the hydrogen fermentation thus resulting in useful products instead of being discarded as waste.
- the acid end products of the hydrogen fermentation e.g. acetate, are re-assimilated in the ABE fermentation to increase the butanol yield and the end product ethanol adds directly to an increased product yield.
- the costs for hydrogen recovery and purification are shared between the ABE fermentation and the hydrogen fermentation which leads to a cost reduction as compared to the two processes separately.
- the costs for energy and/or heat demand are shared by downstream processing of the products after the ABE fermentation and energy and/or heat demand for product recovery after the hydrogen production process.
- thermophilic hydrogen bacteria at circa 70 0 C is that the vegetative cells of the Clostridia will lyse in the hydrogen fermentation and thus add to the supply of nitrogenous nutrients. Clostridia spores, however, remain intact or may germinate. Complete ⁇ aiid controlled germination may be done by a temperature shock to circa 80 0 C which is close to the temperature of thermophilic fermentation, enabling energy saving. The recirculation of heat-treated effluent to the ABE fermentation which runs at a lower temperature leads to a revitalization of the microbial population, thus preventing degeneration of the ABE culture.
- the process of the invention is a zero waste process .
- ABE fermentation are used to indicate the classic acetone- butanol-ethanol fermentation or butanol fermentation or the fermentation to produce any one of acetone, butanol and ethanol or combinations thereof .
- Micro-organisms that are used for performing the various steps in the process according to the invention can be all micro-organisms that can perform the said step, either naturally occurring or genetically modified, and are in particular bacteria and yeasts.
- the present invention will be further illustrated in the Example that follows. The Example is not intended to limit the invention in any way.
- the process of the invention is schematically illustrated in the Figures which show:
- Figure 1 a schematic overview of the process of the invention without ethanol recovery unit.
- FIG. 1 a schematic overview of the process of the invention with ethanol recovery unit.
- a concentrated sugar solution 1, containing 6-8% carbohydrates is loaded into a mixing unit 2.
- the first reaction mixture 4 that is thus obtained contains about 330 mM sugar, K, P,N salts as well as organic nitrogen and trace elements.
- clostridial cells are added to the fermentor 5. The pH at this point is about 6-7.
- This mixture 4 is fed to the ABE fermentor 5.
- the sugar solution 1 can be combined with a mixture 3 that comes from the hydrogen fermentor and contains about 56 mM acetate ⁇ about pH 5-6) and germinating clostridial cells in addition to organic nitrogen and K, P, N salts ⁇ about pH 5-6).
- acetone and ethanol are mainly produced.
- Hydrogen (about 11 L) and CO 2 (about 15 L) are gasses.
- Butanol (about 160 mM) and acetone (about 86 mM) are volatile. These compounds are removed from the reactor 5 by means of gas stripping or any other useful process and in a first product stream 6 fed to a separator or condenser 7 to separate acetone and butanol (11) from the gasses H 2 and CO 2 (12) .
- the second product stream 8 still contains about 33 mM sugars, K, P, N salts, as well as lysed clostridial cells and clostridial spores.
- the pH has dropped to about 5- 6.
- This stream 8 is fed to a hydrogen fermentor 9.
- the fermentor produces about 3 L H 2 and about 1 L CO 2 (13) which are sent to the gas upgrading unit 14.
- the effluent is ptionally heat treated in the heat treatment unit 10 to revitalize the Clostridia spores contained therein and recycled to the first process as stream 3.
- Stream 3 still contains about 22 mM ethanol.
- Figure 2 shows another embodiment that comprises a additional ethanol recovery unit 17.
- the about 22 mM ethanol that is fed to this unit from stream 8 is recovered here.
- Ethanol (about 56 mM) produced in the hydrogen fermentor 9 can also be recycled to this unit to be combined with the ethanol from stream 8 resulting in stream 19 that comprises about 22 + 56 mM ethanol.
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09772349T PL2304021T3 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
EP09772349.8A EP2304021B1 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
DK09772349.8T DK2304021T3 (en) | 2008-07-02 | 2009-06-23 | Process for the combined production of butanol and hydrogen |
CA2728684A CA2728684A1 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
BRPI0913836A BRPI0913836A2 (en) | 2008-07-02 | 2009-06-23 | method for the combined production of butanol and hydrogen |
ES09772349.8T ES2452069T3 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
US13/001,781 US8420358B2 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1035651A NL1035651C2 (en) | 2008-07-02 | 2008-07-02 | Producing butanol and hydrogen from biomass by fermenting biomass to obtain butanol in a first reaction mixture, removing butanol to obtain effluent, and using the effluent as a substrate in a second reaction mixture |
NL1035651 | 2008-07-02 | ||
NL1035905 | 2008-09-08 | ||
NL1035905 | 2008-09-08 |
Publications (1)
Publication Number | Publication Date |
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WO2010000649A1 true WO2010000649A1 (en) | 2010-01-07 |
Family
ID=40941778
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/057802 WO2010000649A1 (en) | 2008-07-02 | 2009-06-23 | Method for the combined production of butanol and hydrogen |
Country Status (8)
Country | Link |
---|---|
US (1) | US8420358B2 (en) |
EP (1) | EP2304021B1 (en) |
BR (1) | BRPI0913836A2 (en) |
CA (1) | CA2728684A1 (en) |
DK (1) | DK2304021T3 (en) |
ES (1) | ES2452069T3 (en) |
PL (1) | PL2304021T3 (en) |
WO (1) | WO2010000649A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015066778A1 (en) | 2013-11-08 | 2015-05-14 | Braskem S.A. | Propene production method |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8927254B2 (en) | 2010-09-29 | 2015-01-06 | University Of Georgia Research Foundation, Inc. | Pyrococcus furiosus strains and methods of using same |
US8962333B2 (en) | 2011-04-04 | 2015-02-24 | University Of Georgia Research Foundation, Inc. | Restriction/modification polypeptides, polynucleotides, and methods |
WO2013120206A1 (en) | 2012-02-17 | 2013-08-22 | Greenfield Ethanol Inc. | Method and system for electro-assisted hydrogen production from organic material |
US9309542B2 (en) | 2012-08-17 | 2016-04-12 | University Of Georgia Research Foundation, Inc. | Recombinant Caldicellulosiruptor bescii and methods of use |
US9587256B2 (en) | 2012-09-06 | 2017-03-07 | University Of Georgia Research Foundation, Inc. | Sequestration of carbon dioxide with hydrogen to useful products |
EP3024940A4 (en) * | 2013-07-26 | 2017-03-29 | Greenfield Specialty Alcohols Inc. | Method and system for production of hydrogen, methane, volatile fatty acids, and alcohols from organic material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002006503A2 (en) * | 2000-07-18 | 2002-01-24 | United States Department Of Energy | Process for generation of hydrogen gas from various feedstocks using thermophilic bacteria |
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2009
- 2009-06-23 US US13/001,781 patent/US8420358B2/en not_active Expired - Fee Related
- 2009-06-23 BR BRPI0913836A patent/BRPI0913836A2/en not_active IP Right Cessation
- 2009-06-23 ES ES09772349.8T patent/ES2452069T3/en active Active
- 2009-06-23 PL PL09772349T patent/PL2304021T3/en unknown
- 2009-06-23 WO PCT/EP2009/057802 patent/WO2010000649A1/en active Application Filing
- 2009-06-23 DK DK09772349.8T patent/DK2304021T3/en active
- 2009-06-23 EP EP09772349.8A patent/EP2304021B1/en not_active Not-in-force
- 2009-06-23 CA CA2728684A patent/CA2728684A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002006503A2 (en) * | 2000-07-18 | 2002-01-24 | United States Department Of Energy | Process for generation of hydrogen gas from various feedstocks using thermophilic bacteria |
Non-Patent Citations (6)
Title |
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CLAASSEN ET AL: "Non-thermal production of pure hydrogen from biomass: HYVOLUTION", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 31, no. 11, 1 September 2006 (2006-09-01), pages 1416 - 1423, XP005601523 * |
DE VRIJE T ET AL: "Glycolytic pathway and hydrogen yield studies of the extreme thermophile Caldicellulosiruptor saccharolyticus", APPLIED MICROBIOLOGY AND BIOTECHNOLOGY, vol. 74, no. 6, 11 January 2007 (2007-01-11), pages 1358 - 1367, XP019513613, ISSN: 1432-0614 * |
EZEJI ET AL: "Bioproduction of butanol from biomass: from genes to bioreactors", CURRENT OPINION IN BIOTECHNOLOGY, vol. 18, no. 3, 8 June 2007 (2007-06-08), pages 220 - 227, XP022110184, ISSN: 0958-1669 * |
LIN ET AL: "Biological hydrogen production of the genus Clostridium: Metabolic study and mathematical model simulation", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 32, no. 12, 16 August 2007 (2007-08-16), pages 1728 - 1735, XP022201192 * |
VAN NIEL E W J ET AL: "Distinctive properties of high hydrogen producing extreme thermophiles, Caldicellulosiruptor saccharolyticus and Thermotoga elfii", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 27, no. 11-12, 1 November 2002 (2002-11-01), pages 1391 - 1398, XP004381765 * |
VAN OOTEGHEM S A ET AL: "Hydrogen production by the thermophilic bacterium Thermotoga neapolitana.", APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY SPRING 2002, vol. 98-100, April 2002 (2002-04-01), pages 177 - 189, XP008006346, ISSN: 0273-2289 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015066778A1 (en) | 2013-11-08 | 2015-05-14 | Braskem S.A. | Propene production method |
US10392315B2 (en) | 2013-11-08 | 2019-08-27 | Braskem S.A. | Propene production method |
Also Published As
Publication number | Publication date |
---|---|
US20110159559A1 (en) | 2011-06-30 |
EP2304021A1 (en) | 2011-04-06 |
CA2728684A1 (en) | 2010-01-07 |
PL2304021T3 (en) | 2014-08-29 |
EP2304021B1 (en) | 2013-12-18 |
US8420358B2 (en) | 2013-04-16 |
BRPI0913836A2 (en) | 2019-09-24 |
ES2452069T3 (en) | 2014-03-31 |
DK2304021T3 (en) | 2014-03-10 |
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