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ENEA Workshop - Bruxelles September 17, 2008
Roberto FarinaAndrea GiordanoAba Aldrovandi
ENEA ACS-PROTIDR Environment, Global Change and Sustainable Development Department,
Bologna, Italy
Pierangela CristianiCESI RICERCA
Environment and Sustainable Development DepartmentMilan, Italy
TECHNOLOGICAL ASPECTS AND PERSPECTIVES OF MICROBIAL FUEL CELLS
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Firenze, 27 Giugno 2008
Bacteria live and Bacteria live and ““workwork””converting the chemical converting the chemical
energy stored in energy stored in renewable biomassrenewable biomass
generating electricitygenerating electricity
Microbial fuel cell technology:what does it mean?
ENEA Workshop Bruxelles September 17, 2008
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Firenze, 27 Giugno 2008ENEA Workshop Bruxelles September 17, 2008
Microbial Fuel Cell (MFC) preliminary remarks
Given the world's limited supply of fossil fuels and fossil fuelGiven the world's limited supply of fossil fuels and fossil fuels' s' impact on climate change, MFC technology's represent a potentialimpact on climate change, MFC technology's represent a potentialfull renewable, carbonfull renewable, carbon--neutral energy for the future.neutral energy for the future.
MFC recover MFC recover valuable resources such as energy and fuel from valuable resources such as energy and fuel from waste and wastewaterwaste and wastewater shifting away from the simple management shifting away from the simple management of treatment biotechnologies.of treatment biotechnologies.
MFC acting as MFC acting as early warning sensors for biological risks early warning sensors for biological risks assessment assessment into the water supply systems and in the water bodies.into the water supply systems and in the water bodies.
MFC could be useful especially in the developing countries for aMFC could be useful especially in the developing countries for adecentralize power production.decentralize power production.
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Firenze, 27 Giugno 2008
Application fieldsApplication fields•• Sensing and control (environment, robotics, Sensing and control (environment, robotics,
securities)securities)•• Remotes areas (sea, lakes, lands)Remotes areas (sea, lakes, lands)•• Industry (waste, wastewater, antifouling)Industry (waste, wastewater, antifouling)•• Medical applicationsMedical applications
Technological productsTechnological products•• SensorsSensors•• New biotechnological processes (bioremediation)New biotechnological processes (bioremediation)•• Low power production Low power production ((AutoAuto--powering devices, powering devices,
medical applications, robotics, antifoulingmedical applications, robotics, antifouling……))•• High power production (wastewater treatments)High power production (wastewater treatments)•• Fuel productions (biohydrogen)Fuel productions (biohydrogen)
Electric power could be not the most valuable Electric power could be not the most valuable ““productproduct””from MFCfrom MFC
Past Present and Future of MFC
ENEA Workshop - Bruxelles September 17, 2008
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Firenze, 27 Giugno 2008
Biofouling growth in sewaterBiofouling growth in sewater
Living micro (and macro) organisms affect industrial cooling cirLiving micro (and macro) organisms affect industrial cooling circuits because cuits because they cause they cause biofouling and microbial corrosion:biofouling and microbial corrosion: deleterious issues deleterious issues incompatible with the plant processes. incompatible with the plant processes.
From electro-active biofilm sensorsto MFC power plants
ElectroElectro--activity of biofilm was firstly used at industrial level againstactivity of biofilm was firstly used at industrial level against biofilm: biofilm: to optimise antifouling treatments in cooling systems of electrito optimise antifouling treatments in cooling systems of electric power c power plantsplants
Corrosion under biofilmCorrosion under biofilm
ENEA Workshop - Bruxelles September 17, 2008
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Firenze, 27 Giugno 2008
Biofilm electrical signal as biosensor
Natural microbes induce an ennoblement of stainless steel corrosNatural microbes induce an ennoblement of stainless steel corrosion potential ion potential due to the increasing of the cathodic process:due to the increasing of the cathodic process:
I
Signal: 10 – 100 μA
Some European studies on Some European studies on microbial corrosion have early microbial corrosion have early demonstrated that the catalysis demonstrated that the catalysis of oxygen reduction by biofilm on of oxygen reduction by biofilm on stainless steel cathodes in water stainless steel cathodes in water environment is an useful environment is an useful mechanism for exploiting of mechanism for exploiting of biofilmbiofilm--based electrochemical based electrochemical sensorssensors
[Mollica 1976][Mollica 1976]
O2 + 4e- → 4OH-
ENEA Workshop - Bruxelles September 17, 2008
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Firenze, 27 Giugno 2008
Biofilm settlement on the Biofilm settlement on the Stainless steel cathode Stainless steel cathode increases the electric current increases the electric current circulating in the probe and circulating in the probe and sustained by zinc dissolutionsustained by zinc dissolution
ZnANODE
Water flow
BIOFILM SENSOR: a simple biofouled bactery
[Mollica and Cristiani 1999][Mollica and Cristiani 1999]
e -
20
40
60
20 21 22 23 24 25 26 27 28 29Days
Sign
al [u
A]
20
40
60
20-ott-97 20-ott-97 21-ott-97 21-ott-97 22-ott-97 22-ott-97 23-ott-97Days
Sign
al [u
A]
20
40
60
20-ott-97 20-ott-97 21-ott-97 21-ott-97 22-ott-97 22-ott-97 23-ott-97Days
Sign
al [u
A]
20
40
60
20-ott-97
21-ott-97
22-ott-97
23-ott-97
24-ott-97
25-ott-97
26-ott-97
27-ott-97
28-ott-97
29-ott-97Days
Sign
al [u
A]
20
40
60
22-ott-97 23-ott-97 24-ott-97 25-ott-97 26-ott-97 27-ott-97 28-ott-97 29-ott-97Days
Sign
al [u
A]
20
40
60
22-ott-97 23-ott-97 24-ott-97 25-ott-97 26-ott-97 27-ott-97 28-ott-97 29-ott-97Days
Sign
al [u
A]
20
40
60
23-ott-97 24-ott-97 25-ott-97 26-ott-97 27-ott-97 28-ott-97 29-ott-97Days
Sign
al [u
A]
Stainless steelCATHODE
ENEA Workshop - Bruxelles September 17, 2008
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Biofilm sensors successfully optimise theantifouling treatments in industrial cooling systems
BenefitsBenefitsChlorine use reductionChlorine use reductionSet up of effective alternative treatment toSet up of effective alternative treatment tochlorinationchlorinationEffective control of microbial corrosion riskEffective control of microbial corrosion risk
ENEA Workshop - Bruxelles September 17, 2008
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An other industrial BIOFILM SENSOR
The electric current circulating in this The electric current circulating in this probe is influenced from the settlement probe is influenced from the settlement of bacteria both on the cathode and of bacteria both on the cathode and anode (different communities)anode (different communities)[[Licina and Nekoksa, 1990]Licina and Nekoksa, 1990]
Anode and cathode made of the same Anode and cathode made of the same materials but differently polarised by materials but differently polarised by external power supply, alternated on the external power supply, alternated on the surface of this probesurface of this probe working inworking inaerobiosis or anaerobiosisaerobiosis or anaerobiosis
Aerobic cathodic: OAerobic cathodic: O22 + 4e+ 4e-- →→ 4OH4OH--
Anaerobic cathodic: HAnaerobic cathodic: H++ →→ HH22
ENEA Workshop - Bruxelles September 17, 2008
H2
↑
Anaerobiosis
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Industrial applications of biofilm sensors operating in Europe and in USA plants
Power plantsDesalination plantsMunicipal incineratorChemical plantsPetrochemical plants…
ENEA Workshop - Bruxelles September 17, 2008
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200
400
600
800
1000
1200
Signal(mV)
04/05 24/05 13/06 03/07 23/07 12/08 01/09 21/09 11/10 (2002)Data0
Chlorinations
Potential applicationsPotential applicationsEarly warning of Early warning of pathogen risks in pathogen risks in
drinking waters and in drinking waters and in industrial water industrial water
circuitscircuits
Alerting homeland Alerting homeland security officials of security officials of chemical attacks on chemical attacks on
drinking water sourcesdrinking water sources
Experimental applications of biofilm sensorsin mineral water plant
Bofilmprobe
coupons
ENEA Workshop - Bruxelles September 17, 2008
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0
0.10.2
0.3
0.40.5
0.6
30/09/06 10/10/06 20/10/06 30/10/06 09/11/06
Sig
nal (
V)
C3-20% water contentC6-40% water contentC9-30% water contentSterilised - 40% water content
SOIL MICROCOSMOS
Biofilm probes
Experimental applications in progress to monitor bioremediation of contaminated soil
[Cristiani et al. 2002][Cristiani et al. 2002]
Potential applicatons:Potential applicatons:process optimisationprocess optimisationin bioremediation ofin bioremediation of
••wastes disposalswastes disposals••LandsLands••waterswaters Biofilm at
Epyfluoresentmicroscopy
ENEA Workshop - Bruxelles September 17, 2008
Firenze, 27 Giugno 2008ENEA Workshop - Bruxelles September 17, 2008
The proportional correlation between the Coulombic yield of The proportional correlation between the Coulombic yield of MFCs and the strength of the wastewater make MFCs possible MFCs and the strength of the wastewater make MFCs possible biological oxygen demand (BOD) sensors. (Kim et al., 2003).biological oxygen demand (BOD) sensors. (Kim et al., 2003).
[Kang et al. (2003)]
Experimental applications of biosensors:Monitoring of oxygen demand in wastewaters
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Firenze, 27 Giugno 2008
Microbial fuel cells:Microbial fuel cells: EElectrons lectrons transfer from colonised transfer from colonised electrodes generating available electrodes generating available electricity useful for external electricity useful for external work work
From signal to power
[Shantaram et al., 2005]
[Rorhback, 1966]
[Rorhback, 1966]
From few From few μμA to ??AmpereA to ??Ampere
ENEA Workshop - Bruxelles September 17, 2008
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Power from marine sediment and seawater:successful laboratory test
ENEA Workshop - Bruxelles September 17, 2008
Bergel et al. 2008, with permission
ISMAR Laboratory Genova
I
Marine sediments Ocean aeratedwater
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Firenze, 27 Giugno 2008
The MFCs were considered to be used for treating The MFCs were considered to be used for treating waste water early in 1991 waste water early in 1991 (Habermann and Pommer, 1991)(Habermann and Pommer, 1991)
Wastewaters plants acting as “microbial power station”
A typical twoA typical two--compartment compartment MFC has an anodic chamber MFC has an anodic chamber and a cathodic chamber and a cathodic chamber connected by a PEM or a salt connected by a PEM or a salt bridge, to allow protons to bridge, to allow protons to move to the cathode while move to the cathode while blocking the oxygen diffusion blocking the oxygen diffusion at the anode.at the anode.
Allen and Bennetto (1993)
From Ampere to WattFrom Ampere to Watt
ENEA Workshop - Bruxelles September 17, 2008
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MFC from wastes and wastewaters
Microbes in the anode Microbes in the anode compartment oxidize compartment oxidize soluble fuel generating:soluble fuel generating:•• electronselectrons•• protonsprotons•• COCO22•• complex biofuels complex biofuels formed from biological formed from biological wastewaste
I
MFCMFCable to removeable to removepollutants from wastes pollutants from wastes and wastewaters and wastewaters generating electrical generating electrical currentcurrent
wastewater, wastesrecalcitrant organics
ENEA Workshop - Bruxelles September 17, 2008
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He et al. (2005)
Liu et al. (2005)
Mohan et al. (2008)
Up-flow MFC
Dual chamber MFC
Single chamber MFC
MFCs design: many different configurations are possible
ENEA Workshop - Bruxelles September 17, 2008
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Methane meter
Wet tip gas flow meter
Aeration pump
Settled sludge recycling pump
Anaerobic recycling pump
Wastewater feeding pump
Data Logger
pHTemp.
Redox SCERedox
Cathode
AnodeAdjustable overfall
1 2 3
4Drain effluent
The MFC assembled at ENEA laboratories in Bologna
MFCs design: reducing the membrane role
ENEA Workshop - Bruxelles September 17, 2008
Microbial fuel cells: best performances reached
Reactor type Fuel used Powerdensity
Powerper volume Reference
(mW/m2) (mW/m3) Two-chamber Landfill leachate 2,060 You et al. 2006 Single chamber Swine waste 261 Min et al. 2005Single chamber Domestic wastewater 103 You et al. 2006
- Hospital watewater 25,000 Rabaey et al. 2005
Single chamber Peptone 269 Heilmann andLogan 2006
Single chamber Glucose 1,540 51,000 Cheng et al. 2006 - Municipal wastewater 10,000 Rabaey et al. 2005
Single chamber Glucose 480 Cheng et al. 2006
Two-chamber Acetate 860 ter Heijne et al.2006
Two-chamber Glucose 5,850 Rosenbaum et al. 2006
Two-chamber Acetate 1,030 Jong et al. 2006Two-chamber Glucose, glutamate 560 102,000 Moon et al. 2006 Upflow Sucrose 29,200 He et al. 2006
ENEA Workshop - Bruxelles September 17, 2008
MFCs: Watt – kW?Stacks of higher numbers of individual
higher numbers of Microbial Fuel Cell have to be connected together to produce useful
levels of power output
With permission
Aelterman et al. (2006)
Shin et al. (2006)
ENEA Workshop - Bruxelles September 17, 2008
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Electricity generation
[Maximum Power Rosenbaum et al., 2006]
[Verstraete, 2008]
Performances
Logan 2008
ENEA Workshop - Bruxelles September 17, 2008
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MFCs to power devices
Moving robots
Ieropoulos et al. (2003, 2006)Raw unrefined fuel
With permission: rotten fruits, dead insects
Anodes containing pure cultures of E. coliO2 cathode MFCs containing sludge microbes4 types of behaviour proved: sensing, processing, communication, actuation
ENEA Workshop - Bruxelles September 17, 2008
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MFCs to power devices
ENEA Workshop - Bruxelles September 17, 2008
UniversityUniversity of Queensland: of Queensland: K. Rabaey and J. KellerK. Rabaey and J. KellerGhent Ghent UniversityUniversity: P. Aelterman, P. Clauwaert and W. Verstraete: P. Aelterman, P. Clauwaert and W. Verstraete
Pilot Plant MFC at Pilot Plant MFC at FosterFoster’’s Brewerys BreweryBirsbarne AustraliaBirsbarne Australia
2 modules of 122 modules of 12tubular open air MFCtubular open air MFCVolume 2.5 mcVolume 2.5 mc
Treatment Treatment 20kgCOD/2.5mc*d20kgCOD/2.5mc*d
Production of 1kW/2.5mcProduction of 1kW/2.5mc
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Firenze, 27 Giugno 2008
MFC to generate new fuel
Applying an external potential Applying an external potential ((≈≈0.25V) by a MFC the cathode 0.25V) by a MFC the cathode potential can overcame the potential can overcame the thermodynamic barrier to produce thermodynamic barrier to produce pure Hydrogenpure Hydrogen
H2G
The MFC can provide the electricity The MFC can provide the electricity used in a second step reactor used in a second step reactor to obtain bioto obtain bio--hydrogen in anaerobiosishydrogen in anaerobiosis
Protons Protons migrated migrated
through the through the electrolyte in electrolyte in the cathodic the cathodic
compartement compartement could be used could be used
to generate to generate HydrogenHydrogen
organic waste wastewaters renewable biomass
ENEA Workshop - Bruxelles September 17, 2008
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Firenze, 27 Giugno 2008
Direct connection of nervous cells might promote the artificial Direct connection of nervous cells might promote the artificial organs organs developments, Brain understanding and repairing.developments, Brain understanding and repairing.Advances MFC using glucose or other physiological fuel in human Advances MFC using glucose or other physiological fuel in human cells might open cells might open new therapies and recover lost physiologic functions.new therapies and recover lost physiologic functions.
Still large development needsStill large development needs••Electrodes efficiency (materials and design)Electrodes efficiency (materials and design)••Membrane removalMembrane removal••External mediators removalExternal mediators removal••Size increasing size decreasingSize increasing size decreasing••SustainableSustainable costcost
Novel ideas for future use of MFC
Advances in nanotechnology and electronics could make it possiblAdvances in nanotechnology and electronics could make it possible to develop e to develop smaller devices that use less energy including: smaller devices that use less energy including:
••unun--toxic electronic microtoxic electronic micro--tracers for environmental usetracers for environmental use••bacterial printsbacterial prints
••medical biotechnologies (Powering pacemedical biotechnologies (Powering pace--makers and other makers and other medical devices). medical devices).
ENEA Workshop - Bruxelles September 17, 2008
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* 09/2008 - Ghent University (Belgium) - Laboratory Microbial Ecology & Technology (LabMET)* 08/2008 - Penn State University (USA) - The Logan Group UPDATE* 08/2008 - SAPIENZA University of Rome - Environmental (Bio)Technology Laboratory* 08/2008 - University of Greifswald (Germany) - Analytical and Environmental Chemistry
* 08/2008 - Technical University of Denmark (DTU) - National Laboratory for Sustainable Energy * 07/2008 - University of Queensland (Australia) - Advanced Wastewater Management Centre (AWMC)
* 07/2008 - Wageningen University (The Netherlands) - Environmental Technology* 07/2008 - Indian Institute of Chemical Technology (India) - Bioengineering and Environmental Centre
(BEEC)* 06/2008 - Harbin Institute of Technology (HIT) (China) - State Key Laboratory of Urban Water Resource and
Environment* 06/2008 - Oregon State University (USA) – Bio-Energy & Environmental Biotechnology (BEEB)* 05/2008 - University of Toulouse - CNRS (France) - Laboratory of Chemical Engineering* 02/2008 - Biodesign Institute at Arizona State University (USA) - The Center for Environmental
Biotechnology (CEB)* 01/2008 - Gwangju Institute of Science and Technology (GIST, Korea) - The Energy and Biotechnology
Laboratory (EBL)* 01/2008 - US Naval Research Laboratory - Washington, D.C. (USA) – The Ringeisen Group* 12/2007 - Newcastle University Microbial Fuel Cell Research group (NEWMFC)* 10/2007 - Harbin Institute of Technology (HIT) (China) - School of Municipal and Environmental Engineering* 09/2007 - Indian Institute of Technology (India) - Environmental Engineering Laboratory* 06/2007 - Universities of Bristol (UoB) & West of England (UWE) - Bristol Robotics Laboratory: Energy
Autonomy Group* 05/2007 - Washington University in St. Louis (USA) - The Angenent Lab
http://www.microbialfuelcell.org/
ENEA Workshop - Bruxelles September 17, 2008
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Conclusive remarks
ENEA Workshop - Bruxelles September 17, 2008