Biotechnology innovations for

renewable energy: direct

bioelectricity generation and
novel biohydrogen generation
technologies.
Bruce Logan, Penn State University

Engineering
Environmental
Institute
 “Energy
Energy isis the
the single
single most
most critical
critical
challenge
environmental facing humanity”
challenge facing humanity
- Nobel Laureate Richard Smalley
 Oil and Fossil Fuels
Existing (coal, oil shale) and new potential energy
Carbon-based alternatives (methane hydrates, coal to
gas) pose continued environmental challenges.

A reduction in CO2 emissions is the main driver for

renewable (CO2-neutral) energy production.
 Energy Utilization in the USA
• US energy use: 97 quad

• US electricity generation: 13 quad

• 5% used for W&WW: 0.6 quad

• Energy needed for H2 for transportation-

Via electrolysis: 12 quad
Using new biomass process: 1.2 quad

97 quad [quadrillion BTUs]= 28,400 terawatt hours

Energy production: Needs to become
more diverse and CO2 neutral
Solar
Wind
Biomass
• Combustion: electricity
• Conventional biotechnology: ethanol,
methane, other value products
• Novel biotechnological approaches: electricity
and hydrogen
 Energy can be recovered in many forms
via biotechnological approaches

• Methane
• Value: $0.43/kg-CH4
• Elevated temperatures required for bioreactors
• Need very long hydraulic detention times (big reactors)

Hydrogen
• Value: $6 /kg, 2.2 × heat value of methane
• Produced-low yield from fermentation from sugars
• Produced from any biodegradable organic matter using the
BEAMR process

Electricity
• Directly generated using microbial fuel cells
Renewable Energy Production

Electricity production using microbial fuel

cells

Overcoming the “fermentation barrier”:

high-yield H2 production from biomass
 Electricity Production in an Aqueous Cathode
Microbial Fuel Cell

load
e -

e-

Fuel
O2

bacteria
(wastes)
H+
Oxidation H2O
products
(CO2) Anode Cathode

Proton Exchange
membrane

Source: Liu et al., Environ. Sci. Technol., (2004)

 Demonstration of a
Microbial Fuel Cell (MFC)
How do electrons reach the electrode?
Carrier (oxidized)

e Carrier (reduced)
Early evidence was that bacteria
produced their own mediators
e - Pseudomonas spp. Produce mediators
such as pyocyanin (Rabaey et al. 2004)
e
- Recent data suggests that Shewanella
spp. use other methods…
e

Bacterium Fe (III)

Mediators produced by
Pseudomonas spp. have distinct
colors.
(Photo provided by Korneel Rabaey,
Ghent University, Belgium; 2005).
 New finding: bacteria use “nano-wires”
Bacterium Electrode

e-

e-

e-

Other bacteria can transfer

electrons directly to the electrode
- Geobacter sulfureducens
- Alteromonas sp.
- Shewanella spp.
Yuri Goby (2005).
“Composition, reactivity and regulation of
extracellular metal-reducing structures
produced by dissimilatory metal-reducing
bacteria.”
Pres. DOE NABIR meeting, April 20, 8:10 am,
Warrenton, VA.
Power densities in laboratory MFCs
Acetate + bacteria (Geobacter metallireducens)

Nafion Proton exchange

membrane MFC
membrane (PEM)

Average Power =40 mW/m2

(vs ~1 mW/m2 w/salt bridge)
 Electrode spacing

Flat Plate, continuous

flow MFC Substrate Power (mW/m2)
Flat Plate 76
(close spacing)
SCMFC 26 - 28
(large spacing)

Single chamber,
continuous flow
MFCs (SC MFC)

Source: Min & Logan, Environ. Sci. Technol. (2004)

MFC- Air cathode systems

- Increase power with air-cathode (oxygen does not need to be

dissolved in water
-Remove proton exchange membrane (PEM)

load
e- e-
Cathode
Anode
Fuel Oxidant
bacteria

(wastes) (O2)
H+
Oxidation Reduced
products oxidant
(CO2) (H2O)
Electricity- Glucose
Power= 494 mW/m2
(No PEM)

0.6
0.5
Power= 250 mW/m2
0.4 (Nafion membrane)
Voltage (V)

0.3
0.2
0.1
0
0 50 100
Time (h)

Source: Liu & Logan, Environ. Sci. Technol. (2004)

 Reduced Electrode spacing 4 cm

& Flow through the Anode

B Outlet X 2 cm Power= 1540 mW/m2
(glucose)

Cathode Anode 1 cm

1600

Power density (mW/m )

A
2
Inlet
1400

1200

1000

800
1 cm
600 2 cm
3 cm
400
0 0.1 0.2 0.3 0.4 0.5 0.6
2
Current density (mA/cm )
Source: Cheng et al. submitted, Environ. Sci. Technol. (2005)
 MFC Reactors
• Aqueous-cathode MFCs: 0.25 yr-- 0.3
mW/m2
– Salt Bridge proton exchange
system
0.5 yr-- 2 mW/m2
– Membrane (Nafion)
• Direct air cathodes MFCs: 1 yr-- 45 mW/m2
– Single Chamber system for
wastewater
1.5 yr-- 500
– Flat plate system mW/m2
– Small batch system for
optimizing electricity generation Current-- 1500
mW/m2
A Path to Renewable Energy
Production

Energy Recovery from

Agricultural wastes-
A Path to Renewable Energy
Production

Energy Recovery from

Wastewater-
Energy content of Wastewaters
Electricity “lost” to water and wastewater
treatment= 0.6 quad (~5% of all electricity)

Energy in wastewater= 0.5 quad

• 0.1 quad of energy in domestic wastewater
• 0.1 quad in food processing wastewater
• 0.3 quad in animal wastes

Wastewater has 9.3× more

energy than treatment
consumes
(Toronto WWTP, Shizas & Bagley (2003)
Potential MFC Power density

Solar energy: 0.1 W/m2 (from 1 W/m2)

WWTP: Current performance of fixed film
wastewater processes equivalent to a power
density of 1 W/m2 total surface area
MFC: 1 m2 of top surface area
– Each “top”-m2 can contain 100 -500 m2 × height
– If 6 m tall 600-3000 m2= 0.6-3 kW
MFC 60 m diameter system=1.7-8.5 MW
Electricity- Domestic Wastewater
0.6 30
P=26 mW/m2 B
0.5 25

Power density (mW/m )

2
Voltage (v)
0.4 20

0.3 15

0.2 10

0.1 5

0 0
0 50 100 150 200
2
Current density (mA/m )

500 30
P (2 cm)

Power density (mW/m )

Coulombic efficiency (%)

2
P= 464 mW/m2 400 P (1 cm) 25

20
B Outlet X 2 cm
300
15

200 10
Cathode Anode
CE (2 cm)
5
100 CE (1 cm)
0
0 0.05 0.1 0.15 0.2
2
Current density (mA/cm )
Inlet
Source: Liu et al., Environ. Sci. Technol., (2004)
Renewable Energy Production

Electricity production using microbial fuel

cells

Overcoming the “fermentation barrier”:

high-yield H2 production from biomass
Current sources for H2
Production
Electrolysis
4%
Coal
18%

Natural Gas
48%

Heavy oils
and naphtha
30%
 Observation: H2 production results primarily
from sugars
300

Biogas:
250

200
- 60% H2
Biogas (mL)

Molasses

150
Potato Starch
Glucose
- 40% CO2
Cellulose

100 Sucrose
Lactate

50

0
0 50 100 150 200 250

Time (h)

Source: Logan, VanGinkel & Oh Environ. Sci. Technol. (2002)

H2 yields: Increase by CO2 removal

100
90
80 H2 Yield increased
70 by 43% with CO2
scrubbing
60
H2, %

50
40
30
20
10
0
0 10 20 30 40 50 60
Source: Park, Hyun, Oh, Logan & Kim, Environ. Sci. Technol. (2005)
 Observation: Lots of waste products,
and not enough acetic acid (best for H2
production)

H2 Acetic glucose
14% 18% Acetic
Butryic
Biomass
Biomass
Butyric
H2
44%
error
 Observation: the “fermentation barrier”

Maximum: 12 mol-H2/mol-
hexose

C6H12O6 + 2 H2O  4 H2 ??????

+ 2 C2H4O2 + 2 CO2

C6H12O6  2 H2 +
C4H8O2 + 2 CO2

Maximum of 4 How can we recover the remaining

mol/mol (2 mol/mol 8 to 10 mol/mol?
in practice)
Overcoming the “Fermentation Barrier”
Bio-Electrochemically Assisted Microbial
Reactor (BEAMR) [Process developed with Ion
Power, Inc.]:
• Acetate: achieve 2.9 mol-H2/mol-acetate
(Maximum of 4 mol/mol)
• Couple fermentation + BEAMR process
→ 8 to 9 mol-H2/mole glucose
• Not limited to glucose
 Essentials of the BEAMR Process
• Conventional MFC:
• Anode potential= -300 mV
• Cathode Potential= +200 mV (+804 mV theory)
• Circuit working voltage= -(-300) + 200= 500 mV
Anode: C2H4O2 + 2 H2O → 2 CO2 + 8 e- + 8 H+
Cathode: O2 + 4 H+ + 4 e- = 2 H2O

• BEAMR Process: No oxygen

• Anode potential= -300 mV
• Cathode potential: 0 mV
• Needed to make H2= 410 mV (theory)
• Circuit (300 mV) augmented with >110 mV= >410 mV
Anode: C2H4O2 + 2 H2O → 2 CO2 + 8 e- + 8 H+
Cathode: 8 H+ + 8 e- → 4 H2
BEAMR Process
PS
CO2 H2
e - e -

Anode Cathode

Bacteria H+

No oxygen:
Cathode
chamber is
kept anaerobic

PEM O2

Source: Liu, Grot and Logan, Environ. Sci. Technol. (2005)

 Potential Needed for
Hydrogen Production
1 -250
Minimum voltage
CD

Current density (A/m 2)

needed is >0.25 V

Anode potential (mV)

0.8 AP -260
(0.11 V theory)
0.6 -270

0.4 -280

0.2 -290

0 -300
0.2 0.4 0.6 0.8 1
Applied voltage (V)

Source: Liu, Grot and Logan, Environ. Sci. Technol. (2005)

 Hydrogen Recovery

110
60%-78% Coulombic
Efficiency (electron recovery) 100

Recovery (%)
90
>90% H2 recovery
80
-Overall: 70
2.9 mol-H2/mol-acetate 60 H2 CE
50
0.2 0.4 0.6 0.8 1
Applied voltage (V)

Source: Liu, Grot and Logan, Environ. Sci. Technol. (2005)

Observation 1: Industries currently “throw away”
a valuable resource (land application)
 Observation 2: Other countries are investing
in development and scale-up of hydrogen
and alternative energy processes

Large-scale biohydrogen
reactor being tested at
Harbin University, China
(Director: Prof. Nanqi Ren)
 CONCLUSIONS

MFCs represent a biotechnological solution to electricity

generation

The BEAMR process can overcome the “fermentation

barrier” and result in high yields of hydrogen from
biomass.

We must develop these technologies, or we risk following

rather than leading in alternative energy development.
Acknowledgements
Previous sponsors:
NSF & EPA TSE (CTS
Program)
USDA-DOE
US Filter

Current research sponsors:

NSF (BES Program): 2004-2007
USDA (2003-2006)
 Thanks to students and researchers in
my laboratory at Penn State!

Top row (left to right): [Bruce Logan], Charles Winslow, Neinke Stein [visiting researcher],
Joshua Middaugh [undergrad], Karl Shellenberger, Garret Estadt [undergrad], David Jones
Bottom row: JungRae Kim, Huilian Ma [postdoc]., Shaoan Cheng [postdoc]., Jenna Heilmann
[graduated], Yi Zuo, SangEun Oh [postdoc].
 Questions ?
Email: blogan@psu.edu
Web page: www.engr.psu.edu/ce/enve/logan.htm
H2E Web page: www.engr.psu.edu/h2e