WO2002097106A1 - Preparation electrochimique d'acide acetique - Google Patents

Preparation electrochimique d'acide acetique Download PDF

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Publication number
WO2002097106A1
WO2002097106A1 PCT/KR2001/001077 KR0101077W WO02097106A1 WO 2002097106 A1 WO2002097106 A1 WO 2002097106A1 KR 0101077 W KR0101077 W KR 0101077W WO 02097106 A1 WO02097106 A1 WO 02097106A1
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WO
WIPO (PCT)
Prior art keywords
acetic acid
electron carrier
bacteria
electrode
clostridium
Prior art date
Application number
PCT/KR2001/001077
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English (en)
Inventor
Woon-Sup Shin
Original Assignee
Bioneer Corporation
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
Priority claimed from KR1020010030198A external-priority patent/KR20020001519A/ko
Priority claimed from KR1020010034857A external-priority patent/KR20020096431A/ko
Application filed by Bioneer Corporation filed Critical Bioneer Corporation
Publication of WO2002097106A1 publication Critical patent/WO2002097106A1/fr

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    • 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
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • 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
    • C12P7/54—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to an electrochemical preparation process for acetic acid. More particularly, the present invention is directed to electrochemical processes for the preparation of acetic acid from carbon dioxide and to electrodes employed for the processes.
  • Carbon dioxide is a major compound that causes green house effect and therefore, is under the control of international rules and negotiation as like the environmental round.
  • the method for treating and reducing the generation of carbon dioxide is laid on the current emergency.
  • Acetic acid can be made from waste gas or waste biomass.
  • Other methods which employ more efficient fermentation process, well-adapting mutation (Gaddy. J. L. US Patent. 5,593,886, January 14, 1997; Grady. J. L.; Chem. G. J. US Patent. 5,821,111, October 13 1998; Gaddy. J. L. US Patent. 5,807,722, September 15, 1998; Schwartz. R. D. US Patent. 4,371,619, February 1, 1983; Brumm. P. J. ; Datta. R. US Patent. 4,814, 273, March 21, 1898; Gaddy. J. L.; Clausen. El Cl US Patent.
  • Clostridium thermoaceticum is known to produce acetic acid from carbon monoxide or carbon dioxide and hydrogen mixture.
  • a process for converting carbon dioxide directly into acetic acid without supplying hydrogen has never been disclosed.
  • an object of the present invention to provide a process for producing acetic acid from carbon dioxide.
  • Another object of the present invention is to provide bacteria combined with electron carrier through covalent bond, which can be employed in the electrochemical process for converting carbon dioxide into acetic acid without causing environmental problem.
  • Yet another object of the present invention is to provide process for combining bacteria with electron carrier to produce bacteria/electron carrier complex catalyst used in electrochemical process for converting carbon dioxide into acetic acid.
  • a still another object of the present invention is to provide an electrode on which bacteria is immobilized, used in electrochemical process for converting carbon dioxide into acetic acid.
  • a still further object of the present invention is to provide an electrode on which bacteria/electron carrier complex is immobilized, used in electrochemical process for converting carbon dioxide into acetic acid.
  • a still further object of the present invention is to provide a method for converting carbon dioxide into acetic acid through electrochemical process which employs bacteria-immobilized electrode.
  • a still further object of the present invention is to provide a method for converting carbon dioxide into acetic acid which employs bacteria/electron carrier/glassy carbon complex electrode.
  • the starting material of the process of the present invention is carbon dioxide and catalyst used therein is enzymes containing CODH in anaerobic bacteria.
  • a proper electron carrier is used and electron is provided through electrodes.
  • the catalyst used in the present invention, CODH can be isolated from various microorganisms.
  • a CODH isolated from Clostridium thermoaceticium is employed as a catalyst.
  • Clos tridium thermoa cetici um is anaerobic homoacetogen which produces acetic acid only.
  • the organism can converts one molecule of glucose (C6) into three molecule of acetic acid (C2); At first, glucose (C6) is degradated into two molecules of pyruvic acid and then, pyruvic acid is converted into one molecule of acetic acid(C2) and one molecule of carbon dioxide (Cl). Then two molecules of carbon dioxide are combined to one molecule of acetic acid by acetyl-CoA pathway.
  • Anaerobes such as Clostridium thermoaceticium have a acetyl-CoA pathway, so called Wood pathway, which produces acetic acid through reduction of two molecules of carbon dioxide and the formation of carbon-carbon bond.
  • the key enzyme is carbon monoxide dehydrogenase (CODH) containing Ni, Fe clusters as active sites.
  • CODH carbon monoxide dehydrogenase
  • Ni, Fe clusters as active sites.
  • CODH carbon monoxide dehydrogenase
  • CODH carbon monoxide dehydrogenase
  • ACS Ragsdale S. W.; Clark, J. E.
  • Clostridium thermoaceticium or carbon monoxide dehydrase (CODH) are stable at 50 to 60 °C, and they reveal good catalytic activities even at high temperature and not affected by the heat generated in the electrical reactions.
  • Clostridium thermoa cetici um and the enzymes isolated therefrom can resist against sulfur compound contained in waste gas from factories, which inactivates common catalysts very easily, they can be used properly for treating carbon monoxide or carbon dioxide discharged together with sulfur compounds .
  • Clostridium thermoaceticium have a good activities toward for CO or H 2 , so it can be employed in treating gas discharged in the form of mixture of CO, C0 2 and H 2 without additional separation process .
  • the electron carrier used in the present invention plays a role of facilitating electron transfer between electrode and biological catalyst, and selected from compounds which can be oxidized or reduced reversibly at electric potential of -300 mV to -700 mV (NHE based on Normal Hydrogen Electrode) .
  • compound of which reduction potential is similar with that of C0 2 , such as alkylviologen which includes methyl viologen, N,N-dimethryl-4, 4' -bipyridyl and derivatives thereof.
  • the compound which can be used as electron carrier in the present invention are tetramethyl viologen, N, N-diethyl-4, 4' -bipyridyl, N,N- diisopropylyl-4, 4' -bipyridyl, and triquat etc., which are 4 , 4' -bipyridyl compound which contains alkyl moiety.
  • Methyl viologen (MV 2+ ) is reduced upon receiving electron from the electrode to form MV + , and then MV "1" transfers electron to Clostridium thermoaceticium or enzymes which contain oxidized CODH and is changed to MV 2+ " The reduced enzymes can reduce C0 2 to CO to produce acetic acid finally.
  • FIG.l of A is acetyl-CoA or Wood pathway showing synthesis of bacterial acetic acid
  • FIG. 1 of B is showing the concept of the present invention of reduction pathway of electrical of carbon dioxide to acetic acid.
  • FIG. 2 is an overview of the apparatus of electrochemical experiments and product analysis of the present invention.
  • FIG. 3 is an overview of the electrochemical cell for electrolysis and cyclic voltammogram of the present invention.
  • FIG. 4 is an overview showing the concept of bonding Clostridium thermoaceticium to DAPV.
  • FIG. 5 is a graph of cyclic voltammogram in the presence of the DAPV bonded to C. t at 55°C. , •
  • FIG. 6 is a graph of electrolysis in the presence of DAPV bonded to Clostridium thermoaceticium at 55°C.
  • FIG. 7 is a graph of reduction of C0 2 by CODH- active DEAE fraction at room temperature.
  • FIG. 8 is a graph of preparation of acetic acid by an example of the present invention at room temperature .
  • FIG. 9 is a graph of cyclic voltammogram of reduction of C0 2 by CODH-active DEAE fraction at 55°C.
  • FIG. 10 is a graph of preparation of acetic acid by an example of the present invention at 55°C.
  • FIG. 11 is a graph of cyclic voltammogram of reduction of C0 2 by CODH-active DEAE fraction at 55°C.
  • FIG. 12 is a graph of the preparation of acetic acid by an example of of the present invention in other condition at 55°C.
  • FIG. 13 is cyclic voltammogram for reduction of C0 2 by crude extracts of Clostridium thermoaceticium .
  • FIG. 14 is a graph of preparation of acetic acid electrolyzed C0 2 in crude extracts of Clostridium thermoa ceticium at 55 °C
  • FIG. 15 is cyclic voltammogram for reduction of C0 2 by Clostridium thermoaceticium at 55°C.
  • FIG. 16 is a graph of electrolysis of C0 2 by an example of the present invention at 55°C.
  • FIG. 17 is schematic diagram of immobilization process of Clostridium thermoaceticium cell on electrode by using cellulose acetate. . >
  • FIG. 18 is Cyclic vlotammogram of C0 2 reduction in the presence of 1.0 mM MV in pH 7.0 phosphate buffer on Clostridium thermoaceticium immobilized glassy carbon electrode by cellulose acetate, at 55 ° C.
  • FIG. 19 is electrolysis of C0 2 reduction in the presence of l.OmM MV in pH 7.0 phosphate buffer on Clostridium thermoaceticium immobilized glassy carbon electrode by cellulose acetate, at 55°C.
  • FIG. 20 is a schematic diagram of immobilization process of DAPV linked cell on electrode by cellulose acetate.
  • FIG. 21 is Cyclic vlotammogram of C0 2 reduction by DAPV linked Clostridium thermoaceticium immobilized copper electrode by cellulose acetate, at 55 ° C.
  • FIG. 22 is graph of electrolysis of C0 2 by DAPV linked Clostridium thermoacetium immobilized copper electrode by cellulose acetate, at 55°C.
  • FIG. 23 is a schematic represent of preparation of carboxyl-terminated glassy carbon electrode and covalent attachment of DAPV and clostridium thermoaceticum on the electrode.
  • FIG. 24 is cyclic vlotammogram of reduction of
  • FIG. 25 is electrolysis of C0 2 clostridium thermoaceticum covalently linked to DAPV-modified glassy carbon electrode (phosphate buffer, PH 7.0), at 55°C.
  • FIG. 26 is stability of cell immobilized by cellulose acetate on gold, copper, GC electrode upon storage in glove box.
  • FIG. 27 is stability of cell immobilezed with DAPV by cellulose acetate on gold, GC electrode upon storage in glove box
  • electrode was linked to the cell by using adaptor with O-ring in order to prevent leakage and influx of the gas.
  • C0 2 was saturated through septum shown in the figure using injection needle.
  • the pH of the solution dropped from 7.0 to 6.3 due to the melted C0 2 when it was saturated with C0 2 .
  • Ag/AgCl(3M NaCl, BAS) was used as a reference electrode which was +0.200 V vs. NHE. All potential values described in the present invention are reported vs. NHE.
  • Proteins were removed from the reagent by using injector filter (Whatman, PVDF) . While this process was carried out, LC used was Youngln Model 910, Shodex, Rspak KC-811(7.8 x 300 mm) column adjusted to 40 °C UV detector (215 nm, Youngln M-720) was used and extraction rate was 1.0 mL/ in in the 0.05 M H 2 S0 4 solution. Meanwhile, acetic acid was also analyzed quantitatively by using GC (gas chromatography; HP5890, FFAP column, FI detector) and the result was similar to that of LC. Also, gas phase reactants and products was analyzed by using GC ( Varian 3700, Pora Q column, TC detector) . After reagents were took out of the glove box by using gas airtight injector by 100 ⁇ 200, «.K, they were injected to GC. In order to analyze quantitatively, previously adjusted CO-checking tool was used.
  • Clostridium thermoaceticium was cultivated in the well-known method that was used widely for cultivating anaerobes (Lundie, L. L. Jr. ; Drake, H. L. J. Bacteriol . 1984, 159, 700-703) and when collecting bacteria, centrifuge bottle and glove box was used to prevent oxygen from damage.
  • Example 2 The reduction of carbon dioxide by using CODH active DEAE fractions at room temperature.
  • the second reaction the formation of H 2 , went well in the condition of low electric potential (more negative) and at the -500 to -600 V reduction of C0 2 occurs without forming H 2 .
  • the formation of H 2 mainly occurred; therefore, the voltage range occurring only reduction of C0 2 , i.e., -550 to -600 mV was selected.
  • Clostridium thermoaceticium is a thermophile and because its optimal growing condition is 55°C, experiment of the example 2 was compared repetitively at this temperature.
  • the electrolysis was carried out and the amount of acetic acid formed by the reduction of C0 2 was compared.
  • acetic acid' was selectively formed at the efficiency of 95 ⁇ 100% and the amount of acetic acid formed was about 25 mM, which was over three times as much as at room temperature. Since 14.3 mM of acetic acid is formed for first 30 min, the rate of the formation of acetic acid is 3.3 umol/min (14.3 mM x 7.0 mL/30 min), which was about 3 times as much as at room temperature.
  • Example 4 was similar to exmaple 3 except using 0.1 mM methyl viologen in order to prevent methyl viologen from being unstabilized.
  • Clostridi um thermoaceticium was distributed into centricon (Amicon, Inc., Centricon YM-30, cut off 30,000) and washed several times with 0.1 M phosphate buffer (pH 7.0). When this solution containing Clostridium thermoaceticium was made homogeneous with a small amount of 0.1 M phosphate buffer, optical density (O.D) was 1.8 at 680 nm, which meant that there were 0.61 g/mL Clostridium thermoaceticium in solution.
  • O.D optical density
  • Methyl viologen used as electron carrier in this experiment was often used as experiment, not only will the pollution of environment be caused, but the activity of Clostridium thermoaceticium also seriously dropped. To minimize these problems, methyl viologen was linked to Clostridium thermoaceticium . If there was any carboxyl group in the surface of
  • DAPV (DAPV) with amine group at the end of the electron carrier was used.
  • DAPV was synthesized according to a method below.
  • methylaminopropylviologen was synthesized (Katz, E. ; de Lacey, A. L. ; Fierro, J. L. G. ; ralacios, J. M. ; Fernandez, V. M. J. Electroanal. Chem. 1993, 358, 247- 259). 10 mmol of 4 , 4' -bipyridine was refluxed with 22mmol of bromoprophylamine hydrobromide in 30 mL of acetonfitrile solution for 12 hours. DAPV crystals obtained after removing suction from solutions were recrystalized three times after adding a small amount of ethanol .
  • Clostridium thermoaceticium was washed with 0.1 M phosphate buffer solution by using centricon.
  • carboxyl group of Clostridium thermoaceti cium N-(3'- dimethylaminoprophy) -N' -ethyl carbodiimide (EDC) was added to solution and then stirred for 30 min.
  • EDC N-(3'- dimethylaminoprophy) -N' -ethyl carbodiimide
  • DAPV was added to solution to make solution homogeneous and then stirred for 30 min.
  • Method for immobilizing enzyme was used to prepare bio-sensor by using glucose oxidase (Maines, A.; Ashworth, D. ; Vadgama, P. Amal. Chim. Acta 1996, 333, 223-231), lactate dehydrogenase, NAD + (sprules, S. d. ; Hart, J. P. ; Wring, S. A. ; Pittson, R. Anal. Chim.
  • Clostridium thermoaceticium was immobilized on electrode by using CA (cellulose acetate) as a physical immobilization method through trapping which uses macromolecules described above.
  • CA cellulose acetate
  • 0.04g CA was added to 4.0 mL toluene/acetone solution (1 : 1 (v/v) ) to make 1% solution. After the solution was dropped on the electrode, it was spreaded and dried for 20-30 min at room temperature. After 0.2 ul of Clostridium thermoaceticium was added on the electrode, 1% CA was added again to prevent bacteria from coming out (FIG. 17) .
  • Clostridium thermoaceticium could be immobilized on the gold, glassy carbon, copper electrode and CV picture was examined in the presence of carbon dioxide. And then, after experiment for formation of acetic acid was carried out, current, the amount of acetic acid formed, and current efficiency were calculated. In the case of glass carbon, reduction current of carbon dioxide was observed (FIG. 18) . As the result of electrolysis at -560 mV, charges consumed during electrolysis for 4 hours were 0.4 C. The amount of acetic acid formed was 0.4 mM and current efficiency was 78% (FIG. 19). In the case of gold and copper electrode, the result was the same as that of described above .
  • Example 11 Clostridium thermoaceticium immobilization by covalent bonding through electron carrier on the surface of glassy carbon electrode and electrochemical transformation of carbon dioxide to acetic acid
  • Clostridium thermoaceticium immobilized electrode by CA After a week, two weeks, four weeks, after storing the electrodes in glove box the experiment for formation of acetic acid was carried out and charge, the amount of acetic acid formed, and current efficiency were measured (electrode was stored in glove box in dried state after washing with 0.1 M phosphate buffer. FIG. 26) . As shown in FIG. 26, current and the amount of acetic acid formed decreased and after two weeks, a half of initial amount was formed. But a small amount of change of current efficiency was changed and this result indicates the fact that although some of bacteria lose their activity but the others can form acetic acid.
  • the advantage of the present invention is; Because biological catalyst is used in order to lower activation energy required when carbon dioxide is reduced into acetic acid, carbon dioxide not only can be selectively transformed to acetic acid, but also pollution of environment can be minimized more effectively.
  • acetic acid is manufactured by using Clostridium thermoaceticium itself, breakage of cells and purification step through column are not required. Therefore, when acetic acid is manufactured in industrial scale, the present invention will help a lot in economical aspect.

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Abstract

La présente invention concerne un procédé de préparation électrochimique d'acide acétique. La présente invention concerne notamment des procédés électrochimiques de préparation d'acide acétique à partir de dioxyde de carbone et des électrodes utilisées pour lesdits procédés.
PCT/KR2001/001077 2001-05-30 2001-06-22 Preparation electrochimique d'acide acetique WO2002097106A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR2001/30198 2001-05-30
KR1020010030198A KR20020001519A (ko) 2000-06-28 2001-05-30 아세트산의 전기화학적 제조 방법
KR2001/34857 2001-06-19
KR1020010034857A KR20020096431A (ko) 2001-06-19 2001-06-19 아세트산 제조용 전극 및 이를 사용하는 아세트산 제조 방법

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011087380A1 (fr) * 2010-01-14 2011-07-21 Lanzatech New Zealand Limited Procédé de production d'un alcool
WO2013074371A3 (fr) * 2011-11-08 2015-06-11 The Regents Of The University Of California Système organique-inorganique hybride pour la production de biocombustibles
WO2016078649A3 (fr) * 2014-11-17 2016-07-21 Gensoric Gmbh Procédé et dispositif de transformation de composés carbonés gazeux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61199792A (ja) * 1985-03-02 1986-09-04 Agency Of Ind Science & Technol 酢酸の製法
JPS62236491A (ja) * 1986-04-04 1987-10-16 Agency Of Ind Science & Technol 酢酸の製造方法
JPH0198472A (ja) * 1987-10-12 1989-04-17 Agency Of Ind Science & Technol 酢酸の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61199792A (ja) * 1985-03-02 1986-09-04 Agency Of Ind Science & Technol 酢酸の製法
JPS62236491A (ja) * 1986-04-04 1987-10-16 Agency Of Ind Science & Technol 酢酸の製造方法
JPH0198472A (ja) * 1987-10-12 1989-04-17 Agency Of Ind Science & Technol 酢酸の製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198642, Derwent World Patents Index; AN 1986-275096 *
DATABASE WPI Week 198725, Derwent World Patents Index; AN 1987-331238 *
DATABASE WPI Week 198921, Derwent World Patents Index; AN 1989-156067 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011087380A1 (fr) * 2010-01-14 2011-07-21 Lanzatech New Zealand Limited Procédé de production d'un alcool
US20110269197A1 (en) * 2010-01-14 2011-11-03 Lanza Tech New Zealand Limited Alcohol production process
AU2011205873B2 (en) * 2010-01-14 2012-09-27 Lanzatech Nz, Inc. Alcohol production process
CN102741417A (zh) * 2010-01-14 2012-10-17 新西兰郎泽科技公司 醇的制备方法
US8377665B2 (en) 2010-01-14 2013-02-19 Lanzatech New Zealand Limited Alcohol production process
KR101317447B1 (ko) 2010-01-14 2013-10-11 란자테크 뉴질랜드 리미티드 알코올 제조 방법
CN102741417B (zh) * 2010-01-14 2016-01-27 朗泽科技新西兰有限公司 醇的制备方法
CN105755058A (zh) * 2010-01-14 2016-07-13 朗泽科技新西兰有限公司 醇的制备方法
CN105755058B (zh) * 2010-01-14 2021-01-15 朗泽科技新西兰有限公司 醇的制备方法
WO2013074371A3 (fr) * 2011-11-08 2015-06-11 The Regents Of The University Of California Système organique-inorganique hybride pour la production de biocombustibles
WO2016078649A3 (fr) * 2014-11-17 2016-07-21 Gensoric Gmbh Procédé et dispositif de transformation de composés carbonés gazeux

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