Biohydrogen production from Solid Phase-

Microbial Fuel Cell (SP-MFC) spent substrate: a

preliminary study.

Dr.Rosa Anna Nastro

Laboratory for Energy and the Environment
Department of Engineering
University “Parthenope” of Naples - Italy
AN INTRODUCTION TO BIOELECTROCHEMICAL
SYSTEMS (BESs)

Biocatalysis

…
Microbial catalysis: exoelectrogenic bacteria

Mn(IV), Fe(III)

Nanowires

Shuttles
MICROBIAL FUEL CELLS (MFCs): PRINCIPLES AND
APPLICATIONS
Bacteria exchange electrons with the anode
in anoxic/anaerobiotic environment Carbon neutral

Electrons flow through an external

circuit Bulk liquid model

Protons pass through a cationic

permeable membrane
Electrons are transferred from
cathode to oxygen
Fuel: organic compounds

No chemical catalysts
Fig.1: Model of a two-chamber MFC.
Environmental temperature
 Organic Solid Waste (OSW) : MFCs?

— Municipal wastewaters

— Industrial wastewaters
— Landfill leachate

— Urine

— Polluted soils
— Composite food
waste
 Organic Fraction of Municipal Solid Waste
(OFMSW)
n About 70% of Municipal Solid Waste
n High moisture content
n Bad smell

Energy input (T=35°C/55°C)

Anaerobic digestion
CH4 and CO2 production

Composting treatment Aeration (energy input)

(aerobic metabolism) Soil conditioner
ANAEROBIC DIGESTION
BIOHYDROGEN PRODUCTION
 RESEARCH QUESTIONS

Anaerobic
Can we combine electrogenesis with dark Digestion or Dark
fermentation and anaerobic digestion of Fermentation ?
solid organic residues?

With what performance?

Solid phase Microbial Fuel Cells set-up (SMFCs)

OFMSW:
§ 78% vegetables
§ 13% fruits SMFC
§ 5% bread n Single-chamber
§ 3% egg shells n Air-cathode
§ 1% other n Membraneless
n Graphite-based electrodes
(AXF-5Q, POCO Graphite Inc.,
Texas, USA) 67cm2 surface
area

Fuel composition: 28% waste, 72% saline solution (Phosphate Buffer Solution, KOH)
 SMFC
pH probe opening
Incubation at 25±2°C for
4 weeks
pH=7,0±0.2
Graphite plates

§ Open Circuit Voltage (mV)

§ Power Density (mW/Kg)
§ Current Density (mA/Kg)
§ Coumbic Efficiency (CE)
SMFC: acquisition data system

Sketch of the equivalent circuit

of the MFCs measurement
chain.
 METHODS: MFC CHEMISTRY AND
MICROBIOLOGY

Organic load removal Standard Methods

(COD, TOC), N, P (2012)

Metabolites Ionic Cromatography

Electroactive
biofilms
 RESULTS: POWER OUPUTS
0,35
0,3 Specific PD:1.75 mWm-2Kg-1
0,25
Maximum CD: 16 mAm-2Kg-1
0,2 1st week

0,15 2nd week Columbic efficiency: 5%*

V

0,1 3rd week

0,05 4th week

0
0 5 10 15 20
-0,05
mA/m-2Kg

2,5

1,5 1st week

2nd week
V

1 3rd week
4th week
0,5

AD energy conversion efficiency accounts 0

0 5 10 15 20
for about 15%. (Bogner et al., 2007) mA/m-2Kg
 OFMSW SMFC: CHEMISTRY
Parameters Units Waste (W) Bioslurry(B) MFC3 Δ MFC3/B

pH 4.9 4.6 7.1 154%

CODsol g L-1 76.1 80.1 30.1 37%

BOD5 g L-1 7.3 8.3 4.4 53%

TOC g L-1 49.6 44.5 17.7 40%

pH= 7.0±0.4

NH4+ mg L-1 95 22 2.1 2%

NO2- mg L-1 5 6 4.3 72%

NO3- mg L-1 194 197 5< 0

Ptot mg L-1 111 76 45.2 41%

Acetate, lactate, formiate, ossalate, succinate present!!
 OFMSW SMFC: BIOFILMS

ANODE: Clostridium tyrobutiricum, Lactobacillus

paracasei, Propionibacterium fraunreichii,
Pseudomonas aeruginosa.

CATHODE: Propionibacterium fraunreichii, Bavariicoccus sp.,

Lactobacillus casei, Lactobacillus paraplantarum, Bacillus spp.
 BIOGAS AND BIOHYDROGEN
PRODUCTION

MFC OFMSW Gas phase

Spent analysis
substrate
Water

Shredding ANAEROBIC DIGESTER (37 °C)

Inoculum
Presser Stirring: 150 rpm

Liquid phase
analysis
 BIOGAS AND BIOHYDROGEN
PRODUCTION

Ø Microbial biomass (OD600)

Ø pH
ØChemical Oxygen Demand (COD)
ØBiogas composition (GC-TCD
detector)
 BIOGAS AND BIOHYDROGEN
PRODUCTION

MFC-SS: 14.13 ml/g

OFMSW: 3.76 ml/g

Fig.2: Cumulative BioH2 production over time. OFMSW:

solid residues from the OFMSW. MFC SS: MFCs Solid
Substrate
 BIOGAS AND BIOHYDROGEN
PRODUCTION

OFMSW: 13.31 ml/g

MFC-SS: 4.56 ml/g

Fig.3: Cumulative methane production over time.

OFMSW: solid residues from the OFMSW. MFC SS:
MFC-Solid Substrate.
 BIOGAS AND BIOHYDROGEN
PRODUCTION

Biomass yield was

higher with OFMSW

pH MFC-SS= 7.15±0.22
pH OFMSW = 4.85±0.9
Fig.5: Biomass concentration trend over time along with
the AD experiment with MFC-SS and OFMSW solid
residues.
 OFMSW MFCs: CONCLUSIONS
MFCs spent substrate revealed to be a better substrate for
BioH2 production than the OFMSW, with a higher yield and an
increasing production over time.
Our calculations report for the SOLE MFC, an energy
production of 20% in comparison to the production and
combustion of methane in engines.
The calculations of MFC+DF and MFC+AD energy production
are in progress.
With further improvements, MFCs can open new possibilities in
the energy recovery from organic waste
 Acknowledgments

This research has been funded by the Italian

Government, with the PON project “Fuel Cell Lab
“Innovative systems and high efficient technologies for
polygeneration” PON03PE_00109_1/F12.”

PON PROJECT 2007-2013 TITLE III

Industrial developement and experimental research project “SMART GENERATION –
Systems and sustainable technologies for energy production
PON03PE_00157_1/F19 -CUP I62E14000010007”
Acknowledgments

Elio Jannelli, Stefano Dumontet, Vincenzo

Pasquale, Mariagiovanna Minutillo, Fabio
Flagiello,

Ciro Florio, Domenico Pirozzi,

Angelo Ausiello, Giuseppe Toscano
Save the date!!

http://www.europeanfuelcell.it/
THANK YOU!!
 Bio-Electrochemical Systems (BESs): a
versatile technology

Membrane

Catalysts

Materials

Configuration

Source of
reducing power

Fig.1: A high-level overview of the concepts associated with bioelectrochemical

systems. (Rabaey K & Rozendal R.A., 2010)
AN INTRODUCTION TO BIOELECTROCHEMICAL SYSTEMS

Microbial Fuel Cells Microbial Electrolysis Cells

 ...AND BACTERIA
Endogenous microflora Mesophilic psicotrophics
acid forming bacteria

Solubility of complex organics:

fats, proteins and carbohydrates Acid forming bacteria in waste
by hydrolysis

Acid formation (oxidation) reaction

4C3H7O2NS + 8 H2O 4 CH3COOH + 4CO2 + 4NH3 + 4H2S + 8H+ + 8 e-

Acetoclastic Electrogenesis?
methanogenesis