WO2007137401A1 - Pile à biocombustible améliorée - Google Patents

Pile à biocombustible améliorée Download PDF

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Publication number
WO2007137401A1
WO2007137401A1 PCT/CA2007/000906 CA2007000906W WO2007137401A1 WO 2007137401 A1 WO2007137401 A1 WO 2007137401A1 CA 2007000906 W CA2007000906 W CA 2007000906W WO 2007137401 A1 WO2007137401 A1 WO 2007137401A1
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WO
WIPO (PCT)
Prior art keywords
cell system
biofuel cell
cathode
anode
protons
Prior art date
Application number
PCT/CA2007/000906
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English (en)
Inventor
Dimitre Gueorguiev Karamanev
Vassili Porfirievich Glibin
Original Assignee
The University Of Western Ontario
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.)
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Publication date
Application filed by The University Of Western Ontario filed Critical The University Of Western Ontario
Publication of WO2007137401A1 publication Critical patent/WO2007137401A1/fr

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/16Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/18Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184Regeneration by electrochemical means
    • H01M8/188Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • BIOFUEL CELL which application was filed in English, and which is incorporated herein by reference in its entirety.
  • the present invention relates to a fuel cell, and more particularly the present invention relates to a biofuel cell based on the microbial regeneration of the oxidant, ferric ions, by the process of aerobic oxidation of ferrous to ferric ions by chemolithotrophic microorganisms that eliminates carbon dioxide from the atmosphere during electricity generation.
  • the slow kinetics of the oxygen reduction reaction on the cathode of the most popular proton-exchange membrane (PEM) hydrogen-oxygen fuel cell is the main reason for both the high cost of the fuel cell itself (requirement of Pt as catalyst) and of low electrical fuel efficiency, around 50% as disclosed in Bockris, J. O.-M. and R. Abdu, J. Electroanal. Chem., 448, 189 (1997).
  • the use of redox fuel cells, in which oxygen is replaced by other oxidants, such as ferric ions, can result in the increase of the rate of cathodic reaction (or exchange current density in electrochemical terms) by several orders of magnitude, as disclosed in Bergens, S. H., G. B. Gorman, G. T. R.
  • the rate of mass transfer of oxidant to the electrode surface is also higher, mainly because of the higher aqueous solubility of the oxidant in redox fuel cells (for example, 50 g/L for Fe 3+ ) as compared to that of oxygen (between 0.006 and 0.04 g/L, depending on the partial pressure and temperature). All these characteristics of the redox fuel cells should theoretically allow efficiencies for the transformation of chemical to electrical energy of 80 to 90% to be achieved using non-noble metal electrodes based on thermodynamic arguments.
  • the main problem in redox fuel cells is the efficiency of reoxidation of the reduced form of the oxidant (oxidant regeneration), see Larsson, R. and B. Folkesson, J. Appl. Electrochem., 20, 907 (1990); and Kummer, J. T. and D.-G. Oei, J. Appl. Electrochem., 15, 619 (1985).
  • the redox potential can reach a value of 1000 mV, see M. Boon, K.C.A.M. Luyben, J.J. Heijnen, Hydrometallurgy, 48 (1998) 1-26. Since the potential of reaction (3) is 1120 mV vs. standard hydrogen electrode (SHE), up to approx. 90% of the reaction energy is used for the production of Fe3+, while the rest (-10%) is available to microorganisms for biomass formation and maintenance.
  • SHE standard hydrogen electrode
  • the present invention provides a redox fuel cell with a method for the oxidant regeneration and which consumes CO 2 .
  • the present invention provides a biofuel cell system, comprising; a) a fuel cell including i) a cathode compartment containing a cathode electrode with an aqueous electrolyte containing a redox couple with a first member of the redox couple in a higher oxidation state than a second member of the redox couple; ii) an anode compartment containing an anode electrode and a fuel having a hydrogen constituent being pumped into said anode compartment, said anode compartment being separated electrically from said cathode compartment; and b) a bioreactor including a vessel enclosing chemolithotrophic metal ion-oxidizing microorganisms, said chemolithotrophic metal ion-oxidizing microorganisms being selected from the group consisting of members of the Leptospirillum genus (excluding Leptospirillum ferrooxidans), members of the Ferroplasma genus, members of the Acidithiobac
  • the biofuel cell is based on the cathodic reduction of ferric to ferrous ions, coupled with the microbial regeneration of ferric ions by the oxidation of ferrous ions, with fuel (such as, but not limited to, hydrogen) oxidation on the anode.
  • the microbial regeneration of ferric ions is achieved by chemolithotrophic microorganisms such as Leptospirillum genus (excluding Leptospirillum ferrooxidans by itself),
  • Ferroplasma genus Acidithiobacillus genus (excluding Acidithiobacillus ferroxidans by itself) and mixtures thereof which may include Leptospirillum ferrooxidans and Acidithiobacillus ferroxidans.
  • Figure 1 shows a diagrammatic representation of a biofuel cell constructed in accordance with the present invention
  • Figure 2 is a plot of cathode potential versus current density achieved with the fuel cell of Figure 1 ;
  • Figure 3 is a plot of cathode potential versus oxidant flow rate into the cathode compartment of the fuel cell of Figure 1 ;
  • Figure 4 is a plot of fuel cell potential versus oxidant flow rate into the cathode compartment of the fuel cell of Figure 1;
  • Figure 5 is a plot of cathode potential versus time for extended operation of the fuel cell of Figure 1.
  • a biofuel cell-bioreactor system shown generally at 10 includes a fuel cell section 12 including a cathodic compartment 14 and an anodic compartment 16 separated by a membrane 18.
  • the anode 20 may be platinized carbon such as platinized carbon felt. Other compounds may be used in addition to platinized carbon including other metals of the platinum group, as well as their mixtures.
  • the anode may also include non-platinum anodic catalysts such as tungsten carbide and other substances containing transition metals, as well as their mixtures. In addition to tungsten carbide, iron phosphide, and cobalt phosphide may also be used as catalysts to mention just a few.
  • Producing the anode from a transition metal compound, and particularly tungsten carbide (WC) is very advantageous because no platinum is required, hence the electrode is much less expensive and it is not poisoned by impurities such as carbon monoxide and sulphur-containing compounds.
  • the transition metal compound is comprised of a powder of the transition metal powder formed into a porous anode electrode structure.
  • the surface of the anode 20 facing the cathode and exposed to the electrolyte can be rendered hydrophobic by applying a hydrophobic material such as teflon to this surface of the anode. Rendering this surface hydrophobic thus prevents ingress of the electrolyte into the anode compartment.
  • the membrane permeable to protons may be a cation exchange membrane (such as for example a Nafion proton-exchange membrane), an anion-exchange membranes, or a combination thereof.
  • the membrane may be a perm-selective membrane conductive to protons but less conductive to metal ions.
  • An example of such a permselective membrane is Selemion produced by Asahi Galss (Japan).
  • the membrane 18 is preferably a proton exchange membrane (PEM) other types of membranes may be used for separating physically the liquid in the cathode compartment 14 from the gas (for example, hydrogen fuel) in the anodic compartment 16.
  • the membrane may also be a composite type of Nafion-Selemion membrane.
  • the membrane 18 does not necessarily need to be a proton-exchange membrane, but it may be a proton-conducting membrane in general.
  • Typical examples include, but are not limited to, a porous, inert, electrically non-conductive material saturated with the electrolyte contained in the cathode compartment (catholyte) which just separates physically the anode and cathode electrodes.
  • Catholyte a porous, inert, electrically non-conductive material saturated with the electrolyte contained in the cathode compartment
  • Non-limiting examples include nitrocellulose membranes with a pore size below 0.2 micrometers; dialysis membranes; reverse osmosis membranes.
  • the membrane can be eliminated, and the anode and the cathode can be separated by the liquid electrolyte.
  • the membrane in the fuel cell may be an ion-exchange membrane.
  • It may also be also a perm-selective membrane, conductive only to certain ions, for example protons, and non-conductive to heavier ions, such as iron ions.
  • a composite containing any of the above-mentioned types of ion-exchange membranes may also be used.
  • the cathode electrode is made from a chemically inert electrically conducting material such as carbon and stainless steel. It will be understood that the cathode may contain a catalyst which may be one of several catalysts, including minute amounts of gold, platinum, tungsten carbide lead, palladium or other catalysts known to those skilled in the art.
  • the cathode electrode may comprise a fibrous layer of a material made of carbon or stainless steel, or in an alternative embodiment the cathode may be a solid plate.
  • the catalyst may be any one of a pure or a mixture with stainless steel, titanium, activated and non-activated carbon powder, and activated and non- activated carbon fibres.
  • a bioreactor 26 is in flow communication with the fuel cell section12.
  • a suitable bioreactor 26 which may be used has been disclosed in D.G. Karamanev, C. Chavarie, R. Samson, Biotechnology and Bioengineering, 57
  • a inverse fluidized bed biofilm reactor may be used as disclosed in D. G. Karamanev, L.N. Nikolov, Environmental Progress, 15 (1996) 194-196.
  • the bioreactor 26 is used for the highly efficient oxidation of ferrous iron ions to ferric iron ions, i.e., for the oxidant regeneration.
  • a bioreactor is a vessel in which microorganisms grow and perform biochemical reactions, such as in the present case ferrous iron oxidation.
  • the bioreactor 26 was inoculated with a mixed culture containing Leptospirillum species and A. ferrooxidans (10% v/v) obtained from a copper mine.
  • the culture media was an aqueous solution containing 0.4 M ferrous ions as sulphate and the nutrient salt composition of Silverman and Lundgren having a pH of 1.8.
  • the latter was circulated with a flow rate of 90 mL/h, using a peristaltic pump, through the cathodic compartment 14 of the fuel cell 10.
  • the anodic compartment 16 was supplied with hydrogen at a rate of 0.3 mL/s, using a peristaltic pump (Cole-Parmer).
  • All the liquids which contact microrganisms should also contain one or more dissolved nutrient salts to facilitate microbial growth.
  • Preferred nutrient salts include: ammonium sulfate, potassium phosphate, magnesium sulfate, potassium chloride, calcium nitrate, calcium chloride.
  • a typical composition of these salts is given by Silverman and Lundgren (J. of Bacteriology, v.77, p.642 (1959)).
  • the liquid in the bioreactor contains any one or combination of inorganic ions such as Ca 2+ , NH 4 + , K + , Mg 2+ , SO 4 2" , NO 3 " , PO 4 3" and Cr.
  • the chemolithotrophic metal-oxidizing microorganisms include members of the Leptospirillum genus (excluding Leptospirillum ferrooxidans by itself), members of the Ferroplasma genus, members of the Acidithiobacillus genus (excluding Acidithiobacillus ferroxidans by itself) and mixtures thereof which may include Leptospirillum ferrooxidans and Acidithiobacill ⁇ s ferroxidans in the mixtures.
  • the members of the Ferroplasma genus may include, but are not limited to, Ferroplasma acidiphilum and Ferroplasma acidarmanus.
  • the members of the Leptospirillum genus may include, but are not limited to,
  • Leptospirillum ferriphilum Leptospirillum thermoferrooxidans, and Leptospirillum . ferrodiazotrophum.
  • the overall reaction (chemical plus biochemical) taking place in the biofuel cell 10, can be obtained by summing the reactions 1 , 6 and 7 which gives:
  • the overall reaction in the biofuel cell 10 is the same as that in a hydrogen-oxygen fuel cell.
  • the microorganisms plus the iron ions simply act as biocatalyst, which greatly increases the rate of the cathodic reaction.
  • the ratio between the amount of energy used for electricity production and the amount of energy used for microbial growth can be easily controlled by varying cultivation conditions such as the ferric-to-ferrous iron concentration ratio in the bioreactor effluent. It is even possible to bring this ratio to infinity by uncoupling the microbial growth from ferrous iron oxidation. In that case no CO 2 is consumed and no biomass is produced.
  • the fuel cell disclosed herein will drastically improve both the economy and environmental effect of fuel cell operation due to the 1 ) increase in the current efficiency; 2) elimination the use of Pt at the cathode; 3) removal of carbon dioxide from atmosphere; and 4)production of potentially highly useful product, single-cell protein.
  • A. ferrooxidans contains 44% protein, 26% lipids, 15% carbohydrates and at least two B-vitamins, see Tributsch, H,
  • the bioreactor containing immobilized mixed culture of chemolitotrophic microorganisms was used to oxidize ferrous ions in batch regime. After reaching about 99% conversion of ferrous iron oxidation, the liquid phase was pumped from the bioreactor 26 to the cathode compartment
  • the biofuel cell operated continuously, without any loss of activity, for 6 months.
  • the fuel cell shown in Figure 1
  • the fuel cell is unique in that it transforms CO 2 into cellular biomass. Therefore, the fuel cell consumes CO 2 from atmosphere during its operation and produces microbial mass, which can be used as single-cell protein (SCP).
  • SCP single-cell protein
  • toxic chemicals can be found in the case when methanol is used as a substrate, see Ravindra, A. P., Biotech. Adv, 18,
  • Microbial contamination (which is sometimes toxic) is eliminated in our technology because there are no known pathogenic microorganisms growing on completely inorganic medium containing high concentrations of iron sulfate at pH between 1 and 2.
  • the microbial contamination is a problem in many of the present methods for SCP production as discussed in Ravindra,
  • the biofuel cell system 10 of Figure 1 requires streams of hydrogen, oxygen and carbon dioxide.
  • the biofuel cell produces electrical energy, heat, water (as vapour) and microbial cell mass.
  • the hydrogen is injected into the anodic compartment of the fuel cell, while the oxygen and CO2 are consumed and water and the biomass are produced in the bioreactor.
  • oxygen and carbon dioxide are supplied from the atmosphere.
  • the biofuel cell has the following characteristics, calculated on the basis of the mass balance, stoichiometry and kinetics: During the generation of 100 kW of electrical energy: 4kg/h H 2 and 4 kg/h CO 2 are consumed; 9 kg/h biomass (SCP) are produced; and 10 m 3 bioreactor is preferred.
  • the major advantages of the proposed biofuel cell to the currently known types of fuel cells are: 1 ) high efficiency (80-90% vs. 50%, respectively); no need for noble- metal cathodes; and the unique feature of the biofuel cell is the consumption of carbon dioxide during its operation production of potentially highly useful product, single-cell protein (SCP).
  • SCP single cell protein
  • the ratio of SCP/electricity can be controlled by either varying the potential of the cathode or by varying the cultivation conditions such as the ratio of Fe 2+7 Fe 3+ concentrations.
  • the present invention is not restricted to only gaseous hydrogen/oxygen fuel cells using gaseous hydrogen fuel but may use other hydrogen containing fuels which can undergo electrochemical oxidation, for example methanol, ethanol, methane to mention just a few.
  • methanol ethanol
  • methane a fuel which can undergo electrochemical oxidation
  • the anodic reaction in the case of methanol fuel is:
  • the anodic reaction of methane as a fuel is:
  • the fuel may be a compound having a hydrogen constituent (either the only constituent in the case of hydrogen gas or one of several constituents in the case of a compound) and electrochemical oxidation of the fuel produces protons and electrons as with the oxidation of hydrogen but may include other products as well, and the fuel is pumped into the anode compartment in a fluid which may be in the form of a gas or liquid.
  • redox couple Fe 2 VFe 3+ and iron-oxidizing microorganisms While the present invention has been illustrated using the redox couple Fe 2 VFe 3+ and iron-oxidizing microorganisms, it will be appreciated by those skilled in the art that other redox couples may be used and metal-oxidizing microorganisms other than those disclosed herein that may be more efficient at oxidizing the member of the redox couple in the lower oxidation state back to the first member of the redox couple in the higher oxidation state.
  • Non- limiting examples of other redox couples include Cu + /Cu 2+ ; Mo 5+ /Mo 6+ as non- limiting examples which can be oxidized by the same microorganisms that can oxidize iron disclosed herein.
  • the terms “comprises”, “comprising”, “including” and “includes” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms “comprises”, “comprising”, “including” and “includes” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un nouveau type de pile à biocombustible, basé sur la régénération microbienne des ions ferriques oxydants. La pile à biocombustible est obtenue par réduction cathodique d'ions ferriques à ferreux, associée à la régénération microbienne des ions ferriques par oxydation des ions ferreux, avec une oxydation du combustible (par exemple de l'hydrogène) sur l'anode. La régénération microbienne des ions ferriques est obtenue par oxydation métallique de microorganismes chimiolithotrophique du genre Leptospirillum (sauf Leptospirillum ferrooxidans seul), d'éléments du genre Ferroplasma, et d'éléments du genre Acidithiobacillus (sauf Acidithiobacillus ferroxidans seul). La génération électrique est associée à la consommation de dioxyde de carbone de l'atmosphère et à sa transformation en cellules microbiennes, pouvant être utilisées comme protéines d'origine unicellulaire.
PCT/CA2007/000906 2006-05-25 2007-05-23 Pile à biocombustible améliorée WO2007137401A1 (fr)

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US60/808,117 2006-05-25

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010068994A1 (fr) * 2008-12-18 2010-06-24 The University Of Queensland Procédé de production de composés chimiques
CN102468510A (zh) * 2010-11-18 2012-05-23 北京科技大学 一种基于杂多化合物储能的间接甲醇燃料电池装置
WO2012069455A1 (fr) * 2010-11-24 2012-05-31 Siemens Aktiengesellschaft Dispositif de stockage d'énergie électrique
EP2462649A1 (fr) * 2009-08-07 2012-06-13 The University of Western Ontario Système de pile à biocombustible
EP2678437A2 (fr) * 2011-02-25 2014-01-01 The Trustees of Columbia University in the City of New York Procédés et systèmes de production de produits en utilisant des ferrobactéries génétiquement modifiées
WO2014055671A1 (fr) * 2012-10-02 2014-04-10 The Board Of Trustees Of The Leland Stanford Junior University Batteries microbiennes comprenant des électrodes à semi-conducteurs ré-oxydables pour la conversion de l'énergie potentielle chimique en énergie chimique

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US6696184B1 (en) * 2000-09-29 2004-02-24 Osram Sylvania Inc. Supported tungsten carbide material
WO2005001981A2 (fr) * 2003-06-27 2005-01-06 The University Of Western Ontario Pile a biocombustible
JP2006012773A (ja) * 2004-03-31 2006-01-12 Mitsubishi Chemicals Corp 燃料電池用触媒及びその製造方法、並びにそれを用いた燃料電池用電極及び燃料電池

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US6589772B1 (en) * 2000-02-29 2003-07-08 Wisconsin Alumni Research Foundation Acidophile archaeal organism
US6696184B1 (en) * 2000-09-29 2004-02-24 Osram Sylvania Inc. Supported tungsten carbide material
WO2005001981A2 (fr) * 2003-06-27 2005-01-06 The University Of Western Ontario Pile a biocombustible
JP2006012773A (ja) * 2004-03-31 2006-01-12 Mitsubishi Chemicals Corp 燃料電池用触媒及びその製造方法、並びにそれを用いた燃料電池用電極及び燃料電池

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010068994A1 (fr) * 2008-12-18 2010-06-24 The University Of Queensland Procédé de production de composés chimiques
CN102282295A (zh) * 2008-12-18 2011-12-14 昆士兰大学 用于产生化学品的方法
JP2012512326A (ja) * 2008-12-18 2012-05-31 ザ ユニバーシティー オブ クイーンズランド 化学物質の生成のためのプロセス
EP2462649A1 (fr) * 2009-08-07 2012-06-13 The University of Western Ontario Système de pile à biocombustible
JP2013501315A (ja) * 2009-08-07 2013-01-10 ザ ユニバーシティ オブ ウエスタン オンタリオ バイオ燃料電池システム
EP2462649A4 (fr) * 2009-08-07 2014-04-23 Univ Western Ontario Système de pile à biocombustible
CN102468510A (zh) * 2010-11-18 2012-05-23 北京科技大学 一种基于杂多化合物储能的间接甲醇燃料电池装置
WO2012069455A1 (fr) * 2010-11-24 2012-05-31 Siemens Aktiengesellschaft Dispositif de stockage d'énergie électrique
US9054366B2 (en) 2010-11-24 2015-06-09 Siemens Aktiengesellschaft Electrical energy storage device
EP2678437A2 (fr) * 2011-02-25 2014-01-01 The Trustees of Columbia University in the City of New York Procédés et systèmes de production de produits en utilisant des ferrobactéries génétiquement modifiées
EP2678437A4 (fr) * 2011-02-25 2015-04-22 Univ Columbia Procédés et systèmes de production de produits en utilisant des ferrobactéries génétiquement modifiées
WO2014055671A1 (fr) * 2012-10-02 2014-04-10 The Board Of Trustees Of The Leland Stanford Junior University Batteries microbiennes comprenant des électrodes à semi-conducteurs ré-oxydables pour la conversion de l'énergie potentielle chimique en énergie chimique

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