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
  • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
  • C12P7/52—Propionic acid; Butyric acids
• • 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
  • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
• • 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 method for manufacturing butanol from butyric acid and hydrogen produced by bacteria using chemical catalysts. More specifically, the present invention relates to a method for manufacturing butanol through ester- ification and hydrogenolysis of butyric acid by chemical catalysts.
• biofuels such as biodiesel and bioethanol are drawing more attentions mostly in advanced countries.
• biobutanol is safer than ethanol-gasoline blend because it reduces vapor pressure when mixed with gasoline.
• it is advantageous over ethanol in that it can be blended with gasoline at a higher proportion, and that biobutanol-gasoline blend can be supplied using existing fuel supply infrastructures.
• an object of the present invention is to provide a method for producing butyric acid and hydrogen by culturing bacteria and manufacturing butanol through chemical catalysis of the butyric acid and hydrogen.
• the present invention provides a method for manufacturing biobutanol comprising: a) pre-treating biomass or organic waste through a process comprising physical grinding, washing and hydrolysis; b) inoculating Clostridium sp.
• bacteria which can produce butyric acid and hydrogen, into the pre-treated carbon sources, culturing under anaerobic condition, and collecting the butyric acid-containing culture medium and hydrogen gas; c) adding butanol equimolar with respect to the butyric acid purified from the culture medium; d) converting the butyric acid and butanol to butyl butyrate by adding a superacid catalyst such as zeolite, heteropoly acids, silica- alumina, Nafion resin (Nafion-H), p-toluenesulfonic acid, SO /ZrO or SO /TiO -
• a superacid catalyst such as zeolite, heteropoly acids, silica- alumina, Nafion resin (Nafion-H), p-toluenesulfonic acid, SO /ZrO or SO /TiO -
• the butanol equimolar with respect to the butyric acid of the step b) is used in the step c).
• the bacteria of the step b) is Clostridium butyricum, Clostridium kluyveri, Clostridium pasteurianum, or Clostridium sp.
• the biomass or organic wastes of the step a) is food wastes, and the washing is carried out using 2 to 2.5 times the volume of water with respect to the food waste.
• the biomass or organic wastes of the step a) are food wastes, and the hydrolysis is carried out for 1-2 days.
• the concentration of the carbon source of the step b) is from 10 to 50 g/L.
• the problem of inhibition of bacterial activity can be prevented because butyric acid-producing bacteria are cultured using organic wastes or biomass as carbon source and butanol is produced by the conversion of the butyric acid through chemical catalysis using hydrogen produced along with butyric acid as byproduct, and, therefore, the productivity and economy of biobutanol production can be improved.
• Fig. 1 is a graph showing the change of hydrogen production rate (•) and pH (O) in a hydrophilic carrier-containing reactor;
• Fig. 2 is a graph showing the change of the concentration of butyric acid (•) and acetic acid (O) in a hydrophilic carrier-containing reactor;
• Fig. 3 is a graph showing the change of hydrogen production rate (•) and pH (O) in a hydrophobic carrier-containing reactor.
• Fig. 4 is a graph showing the change of the concentration of butyric acid (•) and acetic acid (O) in a hydrophobic carrier-containing reactor. Best Mode for Carrying Out the Invention
• the present invention provides a method of culturing bacteria which produce butyric acid and hydrogen using the renewable resources, biomass or organic wastes as carbon source, esterifying the butyric acid produced by the bacteria with butanol using the chemical catalysts and converting it to butyl butyrate, and hydrogenating the butyl butyrate with the hydrogen to produce butanol.
• Clostridium sp.bacteria which are anaerobic bacteria producing butyric acid and hydrogen, are cultured.
• glucose or other pentose or hexose obtained from saccharification of biomass or organic wastes is used as main carbon source.
• the carbon source is included with a concentration of 10 to 50 g/L, preferably 30 g/L.
• the pH of the culture medium is from 5.5 to 7.
• the bacteria are inoculated into the culture medium and cultured in a serum bottle at 30-40 0 C, preferably at 37 0 C, under anaerobic condition while agitating at 200-300 rpm, until the carbon source is almost consumed.
• a continuous bacteria culture system may be operated under the same condition as the batch culture condition of the serum bottle.
• catalysts having outstanding activity and selectivity as compared to conventional catalysts used for similar reaction are used to convert butyric acid into butyl butyrate and produce butanol through hydrogenolysis of butyl butyrate.
• copper- zinc or copper chromite catalyst mainly consisting of copper- zinc or copper-chromium and further comprising barium, magnesium or molybdenum is used as catalyst for esterification and hydrogenolysis.
• the copper- zinc catalyst is very unstable, and the copper-chromium catalyst results in severe environmental problem.
• a superacid catalyst such as zeolite, het- eropolyacids, silica-alumina, Nafion-H (Nafion resin), /?-toluenesulfonic acid, SO /
• ZrO , SO /TiO -La O , or the like is used as the catalyst for esterification of butyric
• a, b, c, d and e are weight fractions (%), a being from 0.1 to 80, b being from 0.1 to 60, c being from 0.1 to 80, d being from 0.1 to 20, and e being from 0 to 5, and Y is W, Pd, Pt, Ru, Cs, Ma, Ca or Ba.
• Example 1 Pre-treatment for saccharification of food wastes (organic wastes)
• the buffering ability was non-existent with little alkalinity. At room temperature, the food wastes were easily degradable and acidic with pH 4.3-4.7. The total solid content was very high as 159-230 g/L. Most of it was volatile solid (137-206 g/L) mostly consisting of organic materials.
• pre-treatment In biological treatment of organic wastes, pre-treatment is required to maximize the solubilization efficiency of organic constituents, reduce the time required for biological hydrogen production through anaerobic fermentation and maximize the efficiency of hydrogen and butyric acid production.
• food wastes should be reduced in size and solubilized for easier utilization as substrates by bacteria, because it consists of relatively large-sized solid particles. Further, the factors that may affect the biological process (toxic substances, specific ionic matters, and the like) need to be reduced or removed.
• Korean food wastes tend to contain a lot of moisture, because of characteristic food culture favoring soups, and be highly biodegradable with very high organic material content, due to be collected separately from the other municipal wastes.
• pre- treatment of food wastes was carried out in order to maximize hydrogen and butyric acid production by physically grinding relatively large-sized materials for easier utilization as substrate by bacteria, and removing substances strongly toxic to the hydrogen- and butyric acid-producing bacteria such as chloride ion, by washing with water.
• solubilization was carried out through hydrolysis by aerobic bacteria, which is one of relatively economical and effective biological treatment methods.
• the chloride ion of the food waste was very high at 9.5 g/L, but it decreased to 1.8, 1.5 and 1.1 g/L when washed with 2, 5 and 10 times the volume of water, respectively.
• a chloride ion content of not greater than 3 g/L is without a toxicity problem on hydrogen and butyric acid production. Therefore, by washing the food wastes with 2 times the volume or more of water, the negative effect caused by the chloride ion can be reduced.
• the amount of discharged gas was measured using a wet gas meter (WN-K 0.5B, Shinagawa). After injecting culture medium, a peristaltic pump was installed to allow recirculation of a certain portion of the medium. Clostridium sp.bacteria were inoculated for the production of butyric acid and hydrogen.
• Sucrose which is typical of the saccharification product of the organic waste produced from the pre-treatment process, was used as substrate for the production of butyric acid and hydrogen.
• a sufficient amount of inorganic materials were included in the water supplied to the bacteria.
• the concentration of sucrose was varied at 5, 15, 25 and 40 g/L in order to examine the effect of the substrate content on the production of butyric acid and hydrogen.
• the contents of the inorganic materials were the same as listed in the following Table 4.
• VFA including butyric acid and ethanol Concentration of VFA including butyric acid and ethanol was measured using Innowax column (30 m x 0.25 mm x 0.25 ⁇ m). Sucrose concentration was measured using a reflect quant strip (sucrose test and lactic acid test strip, Merck Co., Ltd) after taking 2 mL of sample, twice a day. pH was measured using a pH meter (Orion Model 290 A), twice a day.
• Fig. 1 is a graph showing the change of hydrogen production rate (•) and pH (O) in a hydrophilic carrier-containing reactor
• Fig. 2 is a graph showing the change of the concentration of butyric acid (•) and acetic acid (O) in a hydrophilic carrier- containing reactor.
• 14 days were required to reach a stable hydrogen production using a reactor containing a hydrophilic carrier.
• hydrogen content was maintained at about 40%. Initially, HRT was maintained long at 29 hours in order that the bacteria could adhere to the carrier well.
• HRT was reduced gradually from 29 hours to 0.5 hour while gradually increasing recirculation rate from 6 mL/min to 45 mL/min, and the increase of hydrogen production was observed.
• the reactor containing the hydrophilic carrier showed a hydrogen production rate of 4.2 L/L/hr on day 90, and the hydrogen content was maintained approximately at 30%.
• the hydrogen production decreased gradually down to 3 L/L/hr.
• the sucrose concentration was changed to 25 g/L. pH was maintained at 6, and the sucrose conversion ratio was 90% or above.
• the content of butyric acid increased to about 10,000 mg/L.
• sucrose concentration was decreased to 15 g/L. pH was maintained at 6.7-6.8, and the sucrose conversion ratio was maintained at 95%.
• the content of acetic acid increased to about 3,000 mg/L, and the content of butyric acid decreased from about 10,000 mg/L to 6,000 mg/L.
• Fig. 3 is a graph showing the change of hydrogen production rate (•) and pH (O) in a hydrophobic carrier-containing reactor
• Fig. 4 is a graph showing the change of the concentration of butyric acid (•) and acetic acid (O) in a hydrophobic carrier- containing reactor.
• sucrose concentration was set at 25 g/L and HRT was maintained at 20 hours initially, in order that the bacteria could adhere to the carrier well.
• Recirculation rate was gradually increased from 6 mL/min to 50 mL/min, and the sucrose concentration was changed to 40 g/L on day 52.
• the hydrogen production rate was highest at 10.5 L/L/hr.
• the content of acetic acid and butyric acid was about 6,000 mg/L and 12,000 mg/L, respectively. That is, 2 times or more acetic acid and butyric acid were produced than those produced using the hydrophilic carrier-containing reactor up to about 90 days.
• the sucrose concentration was changed to 25 g/L. pH was maintained at 6.3-6.4, and the sucrose conversion ratio was 90% or above.
• the content of butyric acid increased to about 10,000 mg/L.
• the sucrose concentration was decreased to 15 g/L. pH was maintained at 6.5-6.7, as in the hydrophilic carrier-containing reactor, and the substrate conversion ratio was 95% or above.
• the content of acetic acid increased to about 3,000 mg/L, and the content of butyric acid decreased from about 10,000 mg/L to 6,000 mg/L.
• Butyric acid was converted to butyl butyrate using a superacid catalyst SO /TiO -
• reaction temperature was 150-280 0 C
• reaction pressure was 21.4-273.2 atm
• a fixed bed reactor was used for the chemical conversion of butyric acid.
• 2.5 g of the catalyst was filled in the fixed bed reactor and catalysis condition was set as normal pressure and 350 0 C.
• Esterification was carried out while transferring butyric acid into the reactor through a preheating part using a transfer pump under the condition of 200 0C, 35.0 atm and LHSV of 4.5.
• butyl butyrate was hydrogenated in a fixed bed reactor filled with Cu-Co-Zn-Fe-Ca catalyst by supplying hydrogen.
• conversion efficiency to butanol was 88%.

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• 2007
  • 2007-07-06 KR KR1020070068286A patent/KR100879317B1/ko not_active IP Right Cessation
• 2008
  • 2008-07-01 BR BRPI0814011-1A patent/BRPI0814011B1/pt active IP Right Grant
  • 2008-07-01 WO PCT/KR2008/003872 patent/WO2009008616A1/en active Application Filing

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