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WO2008095896A1 - Procédé de récupération de butanol - Google Patents

Procédé de récupération de butanol Download PDF

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Publication number
WO2008095896A1
WO2008095896A1 PCT/EP2008/051342 EP2008051342W WO2008095896A1 WO 2008095896 A1 WO2008095896 A1 WO 2008095896A1 EP 2008051342 W EP2008051342 W EP 2008051342W WO 2008095896 A1 WO2008095896 A1 WO 2008095896A1
Authority
WO
WIPO (PCT)
Prior art keywords
butanol
resin
hypercrosslinked
process according
adsorption
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2008/051342
Other languages
English (en)
Inventor
Einte-Karst Dijk
Van De Maarten Job Graaf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM IP Assets BV
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 DSM IP Assets BV filed Critical DSM IP Assets BV
Publication of WO2008095896A1 publication Critical patent/WO2008095896A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the recovery of a butanol from an aqueous medium.
  • Butanol is an important feedstock chemical and fuel that can be produced by fermentation from renewable biomass by using selected microorganisms.
  • Microorgansims that are able to produce significant amounts of butanol are Clostridium acetobutylicum and Clostridium beijerinckii, which produce butanol during a so-called aceton, butanol, ethanol (ABE) fermentation process.
  • ABE aceton, butanol, ethanol
  • the aim of the invention is an improved process for the recovery of butanol by adsorption, which results in a selective and high overall recovery of butanol from an aqueous medium.
  • the aim is achieved according to the invention by a process for the recovery of butanol from an aqueous medium by adsorbing the butanol to a hypercrosslinked microporous resin. It was surprisingly found that the hypercrosslinked microporous resin in the process according to the present invention showed a high adsorption capacity of and specificity towards butanol, combined with an efficient desorption of butanol from the resin. An efficient desorption of the butanol from the resin is important since it increases the overall recovery of the butanol and allows recycling of the resin.
  • butanol is meant to be n- butanol.
  • the hypercrosslinked microporous resin in the process according to the present invention may be obtained by intensive (post-)crosslinking of polymers present in the resin (see for instance Tsyurupa, M. P. Davankov V.A., Reactive and Functional Polymers (2006) 66: 768-779).
  • a suitable polymer present in the hypercrosslinked microporous resin may for instance be styrene.
  • Crosslinking a polymer, such as styrene, to obtain a hypercosslinked microporous resin according to the present invention may be carried out by any suitable crosslinking agent, for instance ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, allylmethacrylate, divinylbenzene, trivinylbenzene, divinyltoluene, or divinylnaphthalene.
  • the crosslinking agent is divinylbenzene.
  • the concentration of cross-linking agent in the hypercrosslinked microporous resin is preferably at least 2 w/w% and usually below 50 w/w%.
  • the hypercrosslinked microporous resin in the process according to the present invention is a hypercrosslinked styrene-divinylbenzene copolymer (St-DVB) resin, for instance resin is Lewatit® VP OC 1163, Lewatit S 7768, NG-99 or NG-100.
  • St-DVB hypercrosslinked styrene-divinylbenzene copolymer
  • the adsorption capacity of the hypercrosslinked microporous resin such as styrene-divinylbenzene copolymer resin, was at least 250 mg butanol / g resin with a high selectivity towards butanol, and that the butanol was desorbed from the resin efficiently.
  • the hypercrosslinked microporous resin used in the process for the recovery of butanol according to the present invention preferably has an inner surface area of at least 700 m 2 /g, preferably at least 800 m 2 /g preferably at least 900 m 2 /g, preferably at least 1000 m 2 /g, preferably at least 1 100 m 2 /g, preferably at least 1200 m 2 /g, and usually below 1800 m 2 /g, usually below 1600 m 2 /g or below 1500 m 2 /g.
  • the pore volume of the hypercrosslinked microporous resin is between 0.4 - 1 cm 3 /g, preferably between 0.5-0.9 cm 3 /g, more preferably between 0.6-0.8 cm 3 /g.
  • the pore size of the hypercrosslinked microporous resin preferably ranges between 10 and 50 A, preferably between 15 and 40 A, preferably between 15 and 25 A.
  • the hypercrosslinked microporous resin may be in any suitable form, for instance in the form of beads, a membrane, a packed bed or a fluid bed. Preferably the hypercrosslinked resin is in the form of beads.
  • the hypercrosslinked microporous resin may also be applied in combination with pervaporation or perstraction, which are known methods for the skilled person in the art.
  • the hypercrosslinked microporous resin is separated from the aqueous medium after the adsorption of butanol. Separating the hypercrosslinked microporous resin from the aqueous medium may be performed by any suitable method known in the art, for instance by filtration or centrifugation.
  • the butanol is desorbed from the hypercrosslinked microporous resin after the adsorption of butanol.
  • the butanol may be desorbed from the resin by known methods in the art for instance by elution with a suitable eluant, thermal desorption, vacuum desorption or any suitable combination of these methods.
  • Suitable eluents for eluting the butanol from the hypercrosslinked microporous resin are for instance methanol, ethanol, acetone, or propanol.
  • the hypercrosslinked microporous resin When the butanol is desorbed from the hypercrosslinked microporous resin by thermal desorption, it may be preferred to heat the hypercosslinked microporous resin to a temperature near the boiling temperature of butanol. During thermal desorption the hypercrosslinked microporous resin may be heated to a temperature of at least 100 0 C, preferably at least 1 10 0 C, and preferably below 180°C, preferably below 150 0 C, preferably below 140 0 C. It was surprisingly found that at the preferred temperature range the hypercrosslinked microporous resin used in the process according to the present invention was not degraded during thermal desorption of butanol and could be reused in a subsequent butanol recovery process without significant loss of adsorption capacity. In addition it was found that the full amount of the adsorbed butanol could be desorbed from the hypercrosslinked microporous resin completely.
  • the aqueous medium in the process according to the invention may be any suitable medium comprising butanol.
  • the butanol present in the aqueous medium may be the result of a chemical reaction, or it may have been derived from fossil fuels and added to an aqueous medium, or it may have been produced by fermentation.
  • the aqueous medium may be a fermentation medium in which the n-butanol has been produced by microbial fermentation.
  • the present invention relates to a process for the fermentative production of butanol comprising fermenting a microorganism capable of producing butanol in a suitable fermentation medium and recovering the butanol from the fermentation medium by adsorbing butanol to a hypercrosslinked microporous resin.
  • the fermentative production of butanol may be an acetone-butanol-ethanol (ABE) fermentation process.
  • a microorganism capable of producing butanol in an ABE fermentation process may belong to the genus Clostridia, such as Clostridium acetobutylicum or Clostridium beijerinckii.
  • An ABE fermentation is a known process to the skilled person in the art and may be carried out as described by Monot, F. et. a/.1984, Appl. Microbiology and Biotechnology 19:422-425.
  • a microorganism capable of producing butanol may have been made capable of producing butanol by recombinant DNA techniques, for instance as disclosed in WO2007/041269.
  • Microorganisms which have been genetically modified to produce butanol may for instance be a yeast, such as a Saccharomyces cerevisiae, a Lactobacillus, eg. Lactobacillus plantarum, a Bacillus sp., eg. Bacillus subtilis, or an Escherichia coli.
  • Suitable fermentation media for fermenting a microorganism capable of producing butanol are known to the skilled man in the art.
  • the adsorption of butanol from a fermentation medium in the process according to the present invention may be carried out after the production of butanol has been completed (ex situ).
  • the adsorption of butanol to the hypercrosslinked microporous resin may be carried out when the butanol is being produced (in situ).
  • the process for the recovery of butanol from a fermentation medium may also be a combination of ex situ and in situ adsorption.
  • the microbial cells are separated from the fermentation medium before the butanol is adsorbed to the hypercrosslinked microporous resin, to avoid extensive fouling of the resin.
  • butanol recovered by a process according to the present invention as a chemical agent.
  • Butanol may for example be used as raw material for the production of an ester or an ether, a solvent in the organic chemistry, or butanol may be converted to butyl acrylate.
  • Butanol may also be used as a (bio)fuel, for instance as an additive to gasoline or diesel.
  • FIGURES Figure 1 Butanol (squares), acetone (triangles) and ethanol (circles) adsorption isotherms on microporous hypercrosslinked styrene-divinylbenzene copolymer Lewatit® VP OC 1163.
  • Figure 2 Repeated butanol adsorption from an acetone-butanol-ethanol (ABE) fermentation broth (triangles) and water-butanol mixtures (squares). Initial butanol concentration was 3 w/w%. Adsorption capacity expressed is as g butanol / g dried resin.
  • Table 1 Analysis results of liquid butanol concentration in a solution comprising water and microporous hypercrosslinked St DVB resin Lewatit® VP OC 1163.
  • Example 2 Repeated butanol adsorption to hypercrosslinked St DVB copolymer resin
  • the ability to reuse hypercrosslinked PSt DVB resin (Lewatit® VP OC 1 163) was tested with a butanol solution of 3 w/w% in water an in the supernatant of an ABE fermentation broth.
  • the ABE fermentation was carried out according to Monot, F. et. a/.1984, Appl. Microbiology and Biotechnology 19:422-425 using Clostridium acetobutylicum ATCC 35702. After 100 h of incubation the fermentation broth was harvested, and centrifuged at 400Og for 10 min to remove the biomass. The concentration of butanol in the supernatant of the ABE fermentation broth was adjusted to 3 w/w%.
  • the St DVB copolymer resin was reused by adding the St DVB resin to a fresh batches of 3 w/w% butanol -water solution and 3 w/w% butanol ABE-supernatant, respectively, and the adsorption and desorption was determined as described before.

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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 a pour objet un procédé de récupération de butanol à partir d'un milieu aqueux par absorption du butanol sur une résine microporeuse hyper-réticulée. L'invention concerne en outre un procédé de production fermentative de butanol comprenant la fermentation d'un micro-organisme capable de produire du butanol dans un milieu de fermentation approprié et la récupération du butanol à partir du milieu de fermentation par adsorption sur une résine microporeuse hyper-réticulée et l'utilisation du butanol récupéré par un procédé selon la présente invention en tant qu'agent chimique ou (bio)carburant.
PCT/EP2008/051342 2007-02-05 2008-02-04 Procédé de récupération de butanol Ceased WO2008095896A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07101722 2007-02-05
EP07101722.2 2007-02-05

Publications (1)

Publication Number Publication Date
WO2008095896A1 true WO2008095896A1 (fr) 2008-08-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/051342 Ceased WO2008095896A1 (fr) 2007-02-05 2008-02-04 Procédé de récupération de butanol

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WO (1) WO2008095896A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009036076A1 (fr) * 2007-09-11 2009-03-19 Tetravitae Bioscience, Inc. Procédé pour la production de solvant à l'aide d'adsorption en phase liquide
WO2010012660A1 (fr) * 2008-07-31 2010-02-04 Shell Internationale Research Maatschappij B.V. Procédé de fabrication d'un alcool
WO2012016450A1 (fr) * 2010-08-06 2012-02-09 南京工业大学 Procédé de séparation du butanol
WO2013004009A1 (fr) * 2011-07-05 2013-01-10 南京工业大学 Procédé pour la désorption et la régénération d'adsorbant polymère macroporeux hydrophobe adsorbant le butanol
WO2012141546A3 (fr) * 2011-04-14 2013-03-07 지에스칼텍스(주) Appareil et procédé de séparation et de raffinage de fermentation de produit fabriqué par fermentation de micro-organismes à l'aide d'adsorbant
WO2016205014A1 (fr) * 2015-06-17 2016-12-22 Exxonmobil Research And Engineering Company Matériaux adsorbants contenant un zif et leurs utilisations

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
L. NIELSEN ET.AL.: "Adsorbents for extractive bioconversion applied to the acetone-butanol fermentation", APPL.MICROBIOL. BIOTECHNOL., vol. 28, 1988, pages 335 - 339, XP009087621 *
LIU F ET AL: "Separation of acetone-butanol-ethanol (ABE) from dilute aqueous solutions by pervaporation", SEPARATION AND PURIFICATION TECHNOLOGY, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 42, no. 3, April 2005 (2005-04-01), pages 273 - 282, XP004773276, ISSN: 1383-5866 *
M.P.TSYURUPA ET.AL.: "Porous structure of hypercrosslinked polystyrene: State-of-the-art mini-review", REACTIVE & FUNCTIONAL POLYMERS, vol. 66, 2006, pages 768 - 779, XP002445013 *
N. QURESHI ET.AL.: "Energy-efficient recovery of buanol from model solutions and fermentation broth adsorption", BIOPROCESS BIOSYST. ENG., vol. 27, 2005, pages 215 - 222, XP002445012 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009036076A1 (fr) * 2007-09-11 2009-03-19 Tetravitae Bioscience, Inc. Procédé pour la production de solvant à l'aide d'adsorption en phase liquide
WO2010012660A1 (fr) * 2008-07-31 2010-02-04 Shell Internationale Research Maatschappij B.V. Procédé de fabrication d'un alcool
US20130158303A1 (en) * 2010-08-06 2013-06-20 Hanjie Ying Method for separating butanol
WO2012016450A1 (fr) * 2010-08-06 2012-02-09 南京工业大学 Procédé de séparation du butanol
US8766019B2 (en) * 2010-08-06 2014-07-01 Nanjing University Of Technology Method for separating butanol
AU2012243504B2 (en) * 2011-04-14 2015-08-13 Gs Caltex Corporation Apparatus and method for separating and refining fermentation of product manufactured by fermenting microorganism by using adsorbent
WO2012141542A3 (fr) * 2011-04-14 2013-03-07 지에스칼텍스(주) Appareil et procédé de séparation et de raffinage de fermentation de produit fabriqué par fermentation de micro-organismes à l'aide d'adsorbant
WO2012141546A3 (fr) * 2011-04-14 2013-03-07 지에스칼텍스(주) Appareil et procédé de séparation et de raffinage de fermentation de produit fabriqué par fermentation de micro-organismes à l'aide d'adsorbant
US10150973B2 (en) 2011-04-14 2018-12-11 Gs Caltex Corporation Apparatus and method for separating and refining product manufactured by microbial fermentation by using adsorbent
US20140155658A1 (en) * 2011-07-05 2014-06-05 Hanjie Ying Method for desorbing and regenerating butanol-adsorbing hydrophobic macroporous polymer adsorbent
WO2013004009A1 (fr) * 2011-07-05 2013-01-10 南京工业大学 Procédé pour la désorption et la régénération d'adsorbant polymère macroporeux hydrophobe adsorbant le butanol
US9108897B2 (en) 2011-07-05 2015-08-18 Nanjing University Of Technology Method for desorbing and regenerating butanol-adsorbing hydrophobic macroporous polymer adsorbent
WO2016205014A1 (fr) * 2015-06-17 2016-12-22 Exxonmobil Research And Engineering Company Matériaux adsorbants contenant un zif et leurs utilisations
US9919288B2 (en) 2015-06-17 2018-03-20 Exxonmobil Research And Engineering Company ZIF-containing adsorbent materials and uses thereof

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