cellulose conversion to hydrogen and electricity
TRANSCRIPT
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Cellulose Conversion to Hydrogen and ElectricityCellulose Conversion to Hydrogen and Electricity
Jay ReganAssistant Professor
Department of Civil & Environmental EngineeringPenn State University
Jay ReganAssistant Professor
Department of Civil & Environmental EngineeringPenn State University
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de Groot (2003). In: Bio-Methane & Bio-Hydrogen.
Biomass to Secondary Energy Carriers
microbial fuel cells
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1) Fermentative production of H2 from sugars
• Full oxidation of glucose to H2:
C6H12O6 + 6 H2O 12 H2 + 6 CO2
• Known pathways:
C6H12O6 + 2 H2O 4 H2 + 2 C2H4O2 + 2 CO2
C6H12O6 2 H2 + C4H8O2 + 2 CO2
• Typical yield < 2 mol H2/mol glucose
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Cellulosic biomass is more recalcitrant to biological treatment
(DOE, 2006)
Cellulose Cellobiose Glucose
Hydrolysis of Cellulose
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Inoculum H2 Yield Reference(mol/mol hexose)
Clostridium cellulolyticum 1.66 (6.7 g/L initial) Desvaux et al (2000)
0.33 (29.1 g/L)
Heat-shocked sludge 0.36 (12.5 g/L) Lay et al (2001)
0.08 (50 g/L)
Heat-shocked soil 0.005 (4.0 g/L) Logan et al (2002)
Activated sludge 0.07 (5.0 g/L) Liu et al (2003)
Cellulose-derived hydrogen:
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• Clostridium speciesacetobutylicum, cellulolyticum, cellobioparum, celerecrescens, populeti, phytofermentans
• SubstratesCellobiose (disaccharide)MN301 cellulose (mixture of amorphous and crystalline ) Avicel (microcrystalline)
• AnalysesBiogas, Hydrogen, CO2, Biomass protein, Substrates,
Fermentation products
Characterization of Cellulolytic, H2-Producing Clostridia
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Gas production from cellobiose
0
5
10
15
20
25
30
0 1 2 3 4 5 6 7 8 9 10
day
H2(
mL)
C.acetobutylicumC.cellulolyticumC.cellobioparumC.celerecrescensC.populetiC.phytofermentans
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H2 yield comparison
Ren, Ward, Logan, and Regan (2007) J. Applied Microbiol.
0.0
0.5
1.0
1.5
2.0
2.5
MN301 Avicel Cellobiose
Hyd
roge
n Y
ield
(mol
hyd
roge
n m
ol-1
Hex
ose)
Clostridium species: acetobutylicum, cellulolyticum, cellobioparumcelerecrescens, populeti, phytofermentans
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H2 production rates
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
MN301 Avicel Cellobiose
Hyd
roge
n pr
oduc
tion
rate
s(m
l hyd
roge
n m
g-1 p
rote
in d
ay-1
)
Ren, Ward, Logan, and Regan (2007) J. Applied Microbiol.
Clostridium species: acetobutylicum, cellulolyticum, cellobioparumcelerecrescens, populeti, phytofermentans
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CathodeAnode
PEM
Fuel (cellulose)
CO2
Fe(CN)63-
Fe(CN)64-
H+
e- e-
2) Microbial fuel cells for production of electricity from biodegradable organic matter
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Electricity production by the binary culture on cellulose
Co-culture can be used to make electricity from cellulose
• Clostridium cellulolyticum– Converts cellulose to H2 and
volatile acids – Can not produce electricity
• Geobacter sulfurreducens– Produces electricity from
acetate and H2– Can not degrade cellulose
Ren, Ward,and Regan (2007) ES&T
Hours0 200 400 600 800 1000 1200 1400 1600 1800
Pow
er D
ensi
ty (m
W/m
2 )
0
20
40
60
80
100
120
140
160G.sulfurreducens C.cellulolyticum
B
2g/LCMC1g/LCellobiose
8mM Acetate 12.3 mM Acetate
1g/LCMC
Neither pure culture produced electricity on cellulose
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Co-culture achieved comparable power on CMC as Geobacter on acetate
0
20
40
60
80
100
120
140
160
180
0.00 0.02 0.04 0.06 0.08 0.10Current density (mA/cm2)
Pow
er d
ensi
ty (m
W/m
2 )
Geobacter on acetate (154 mW/m2)
Co-culture on CMC (143 mW/m2)
Co-culture on MN301+ NaCl (67.9 mW/m2)
Co-culture on MN301 (59.2 mW/m2)
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H0 200 400 600 800 1600 1800
Pow
er D
ensi
ty (m
W/m
2 )
0
10
20
30
40
50
60
2g/L CMC
1g/L CMC 1g/L MN301
Hours0 200 400 600 800 1600 1800
Pow
er D
ensi
ty (m
W/m
2 )
0
10
20
30
40
50
60
2g/L CMC
1g/L CMC 1g/L MN301
Max. Power: Enhanced MFC: 53.8mW/m2
Sludge only MFC: 40.8mW/m2
Electricity from cellulose: undefined mixed culture
Ren, Ward,and Regan (2007), ES&T
• Inoculum is wastewater (bacteria naturally present in the environment)
• C. cellulolyticum enhanced power production:
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Electricity from cellulose and chitin in a sediment MFC
SeawaterCathode
AnodeMarine Sediment
Chitin 80 Chitin 20
Carbon cloth filled with Chitin 80
CelluloseTime (hr)
0 50 100 150 200 250 300
Pow
er D
ensi
ty (m
W/m
2 )
020406080
100120
Rep 1Rep 2Rep 3
Time (hr)
0 50 100 150 200 250 300
Pow
er D
ensi
ty (m
W/m
2 )
0
20
40
60
80
100
Chitin80 Chitin20 Control
Cellulose
Chitin
Rezai, Richard, Brennan and Logan, ES&T (2007)
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Microbial identification by fluorescent in situhybridization (FISH)
Suspended sample of coculturefrom CMC-fed MFCGeobacter (yellow/red) - Clostridium (green)
Geobacter (SRB385)
Clostridium (SYTO 9)
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Summary
• C. cellulolyticum and C. populeti showed the highest hydrogen production rates and yields from solid cellulose
• H2 yields (~1.6 mol/mol) comparable to typical values with glucose, but rates were only 50-70% that of cellobiose
• Cellulose conversion to electricity is possible in microbial fuel cells through pairing of cellulolytic and anode-reducing phenotypes
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Co-PIs:Bruce Logan (Civil and Environmental Engineering)Mark Guiltinan (Horticulture)
Students/Post-docs/Research Associates:Zhiyong Ren, Thomas Ward, Sang-Eun Oh, Shaoan Cheng, David Jones
Funding:USDA/DOE 2003 Biomass Research and Development Initiative