improving hydrogen efficiency during thermochemical ... · pdf filepresentation_namefor the...
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November 4, 2015
Abhijeet P Borole 1,3, Alex Lewis3, Spyros Pavlostathis2, Xiaofei Zeng2, Costas Tsouris1,2, Shoujie Ren3, Philip Ye3, Pyongchung Kim3, Niki Labbe3
1Oak Ridge National Laboratory 2Georgia Institute of Technology 3University of Tennessee
Improving Hydrogen Efficiency During Thermochemical Conversion of Biomass to Fuels
2 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
Overview
• Hydrogen Requirement in Thermochemical Biofuel Pathway • Microbial Electrolysis Technology (MEC) • Prevent Organic Carbon Loss via Aqueous Phase • Potential to Improve Process Efficiency via Energy
Recovery • Address Separations and Unit Operations to Support MEC • Discuss Potential for Carbon and Separations Efficiency
Improvement in Bio-oil Pathways
3 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
TC Pathway – Role of MEC
Microbial Electrolysis
Biomass
Energy/ Potential
Bio-oil Upgrading
and Hydrotreat
ment Hydrocarbon fuels
Pyrolysis
Hydrogen
Oil phase
Aqueous Phase
Bio-oil
Problem Statement • Deoxygenation of
biomass
• Need for hydrogen to make HC fuels
• Loss of carbon to aqueous phase
Goals • Develop technology for
hydrogen production in biorefinery to facilitate biomass deoxygenation.
• Reforming of aqueous phase organics to hydrogen via microbial electrolysis cell (MEC) technology.
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Microbial Electrolysis • Hydrogen production from pyrolysis-derived
aqueous phase – Address aqueous carbon emulsified with oil
phase – acidic and polar molecules – Causes instability of bio-oil – Corrosivity of bio-oil
• Carbon, Hydrogen and Separations Efficiency for Bio-oil Pathways program (CHASE)
• Microbial electrolysis – Conversion of bio-oil aqueous phase (BOAP)
organics to hydrogen – Anode: Conversion of degradable organics to
electrons, protons and CO2
– Cathode: Proton reduction to hydrogen at applied potential of 0.3-1V.
– Uses electroactive biofilms capable of direct electron transfer
H2
H+ Organic Carbon
CO2 + H2O
Bio
cata
lytic
ano
de
e- e-
CxHyOz → CO2 + H+ + e- H+ + e- → H2
Nutrients
Cell mass
Cat
hode
> 0.3 V
Cathode catalyst
H+
H+
H+
H+
MEC
Biotechnol for Biofuels., Controlling accumulation of fermentation inhibitors in biorefinery process water using Microbial Fuel Cells, Borole, A. P., et.al., 2009, 2, 1, 7. Energy Environ. Sci., Electroactive biofilms: Current status and future research needs Borole, A. P., et al., 2011, 4: 4813-4834.
Pathway: Bio-oil Aqueous Phase (BOAP) → electrons + protons (anode ) → H2 (cathode)
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Integrated Pyrolysis-Microbial Electrolysis
Pyrolysis Oil-water Separation
Bio-oil
Aqueous phase Microbial
Electrolysis
Bio-oil Upgrading
+ -
Liquid Fuels
Renewable Hydrogen
H2
Lewis, A. J., et al. (2015). "Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process." Bioresource Technology 195: 231-241.
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• Feedstock: switchgrass • Particle size: less than 2mm • Water content of switchgrass: 7-8 wt%. • Feeding rate: 10kg/hr • Reaction temperature: 500°C • Bio-oil: combined by three condensers • Add water to bio-oil (4:1 ratio) to
separate aqueous fraction.
Pilot auger pyrolysis reactor at UTK Center for Renewable Carbon
Bio-oil production process scheme
Bio-oil produc-
tion
Bio-oil yield (wt%)
Bio-char yield (wt%)
Non-condensable gas yield (wt%)
1st batch 50 29 21
2nd batch 54 29 17
Products from switchgrass pyrolysis
Production of bio-oil from switchgrass
Bio-oil production
Ren, S., X. Ye, Borole, A P., Kim, P; Labbe, N (2015). "Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a pilot-scale auger pyrolyzer." J. Anal. Appl. Pyrolysis, manuscript in review.
7 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
Bio-oil Aqueous Phase characterization…
Classifications Major compounds Concentration in aqueous phase(g/L) Method
Carboxylic acid Acetic acid 11.96 HPLC Propionic acid 1.89 HPLC Vanillic acid 2.69 HPLC
Sugars Levoglucosan 15.33 HPLC
Furans Furfural 1.01 HPLC HMF 0.54 HPLC 2(5H)-Furanone 1.17 GC
Alcohols 1,3-propanediol 1.84 GC 1-hydroxybutanone 1.35 GC
Aldehydes and ketones
Cyclohexanone 0.07 GC 3-methyl-1,2-cyclopentanedione 0.46 GC
Phenols and alkyl phenols
1,2-benzendiol 1.77 HPLC Phenol 1.8 HPLC 2-methoxyphenol 0.25 GC 2-methyl-4-methyphenol 0.07 GC 2,6-Dimethoxyphenol 0.26 GC 3-ethylphenol 0.56 GC
Sum 43.01 Ren, S., X. Ye, Borole, A P., Kim, P; Labbe, N (2015). "Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a pilot-scale auger pyrolyzer." J. Anal. Appl. Pyrolysis, manuscript in review.
8 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
Anode Biocatalyst Development
• Growth of electroactive biofilms for conversion of BOAP compounds.
• Goals – Tolerance to phenols and furan aldehydes – Optimize population diversity
• Approach – Use of optimized system (MFC) configuration – Use of previously optimized process
parameters.
US Patent 7,695,834, UT-Battelle, Borole, A. P., USA, 2010. US Patent 8,192,854 B2 UT-Battelle, Borole, A. P., USA, 2012. Energy Environ. Sci., Borole, A. P., et al., 2012, 4: 4813-4834. Bioresour. Technol. Borole, A. P., et al., 2011, 102, 5098. Biochem. Eng. J. Borole, A. P., et al., 2009, 48, 71.
Microbial Diversity In Biofilms
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lev
oglu
cosa
n
ace
tic a
cid
p
ropi
onic
aci
d
1-h
ydro
xybu
tano
ne
HM
F
12-
benz
endi
ol
2
(5H)
-fur
anon
e
van
illic
aci
d
phe
nol
f
urfu
ral
gua
iaco
l
3-e
thyl
phen
ol
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 Retention Time [min]
0
20000
40000
60000
Inte
nsity
b0-T0 - CH9b0-T1 - CH9b0-T3 - CH9
Conversion of Switchgrass Bio-oil Aqueous Phase to Hydrogen
Conversion of organics in BOAP using evolved bioanode:
0 h 24 h 72 h
Batch experiment, BOAP loading = 0.1 g/L, HPLC-Photodiode array
Successful development of anode biocatalyst for conversion of switchgrass bio-oil aqueous phase, including removal of acetic acid and phenolic acids.
1. Source of inoculum 2. Pure culture vs. consortium
3. Gram-positive vs. Gram-negative Biofilm parameters (Dependent variables)
Process/ Operating parameters
Biological parameters
Electroactive Biofilm Optimization
1. Batch vs. flow system
2. External resistance
3. Redox potential 4. Shear rate /
liquid flow rate 5. pH 6. Substrate
loading 7. Temperature 8. Aerobic vs.
anaerobic 9. Ionic strength
1. Electrode spacing 2. Presence of
membrane and type of membrane
3. Relative anode:cathode surface area
4. Electrode surface area to volume ratio
5. Electrode properties: conductivity, hydrophilicity, porosity, etc.
6. Type of cathode (oxygen diffusion)
1. Biofilm growth rate 2. Specific rate of electron transfer 3. Ability to synthesize redox-active mediators 4. Ability to grow nanowires and perform DET
System design parameters
5. Relative exoelectrogen population 6. Characteristics of EPS layer 7. Extent of substrate mineralization 8. Substrate specificity
Energy Environ. Sci. (Review paper) Electroactive Biofilms: Current Status and Future Research Needs, Borole AP, Reguera G, Ringeisen B, Wang Z, Feng Y, Kim, BH, 2011, 4:4813-4834
MEC optimization is a complex process, requiring system design, process and biological parameter optimization.
11 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
H2 production from BOAP – Batch Run • 0.1 to 0.3 g/l batch BOAP
• 12-24 hour experiment
Demonstrated an yield of hydrogen of ~ 70% from bio-oil aqueous phase.
0123
0 0.1 0.2 0.3 0.4H2 P
rodu
ctiv
ity L
/L/d
Concentration (g/l)
H2 Productivity L/L-anode-day
63a
63b
0%
20%
40%
60%
80%
100%
0.1 g/l 0.2 g/l 0.3 g/l
Anode Coulombic Efficiency (CE)
0%
20%
40%
60%
80%
100%
0.1 g/l 0.2 g/l 0.3 g/l
Cathode Efficiency
0%
20%
40%
60%
80%
100%
0.1 g/l 0.2 g/l 0.3 g/l
Hydrogen Yield from Bio-oil Aqueous Phase
Lewis, A. J., et al. (2015). "Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process." Bioresource Technology 195: 231-241.
12 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
H2 production from BOAP – Continuous Run • 2 g/l/d to 10 g/l/d continuous BOAP feed
• 12-24 hour experiment
Demonstrated an yield of hydrogen of ~ 80% from bio-oil aqueous phase.
0%
20%
40%
60%
80%
100%
2 g/l/d 4 g/l/d 10 g/l/d
Anode CE
0%
20%
40%
60%
80%
100%
2 g/l/d 4 g/l/d 10 g/l/d
Cathode Efficiency
0%
20%
40%
60%
80%
100%
2 g/l/d 4 g/l/d 10 g/l/d
H2 Yield
0
2
4
6
0 5 10 15H2 P
rodu
ctiv
ity L
/L/d
Loading rate (g/l/d)
H2 Productivity
Lewis, A. J., et al. (2015). "Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process." Bioresource Technology 195: 231-241.
13 Managed by UT-Battelle for the U.S. Department of Energy Presentation_name
Novelty of Bioelectrochemical Systems
1. Biological electron transfer and electroactive biofilm development
2. Biocatalysis/Electrocatalysis synergy
3. Diversification potential Substrate
Product / Fuel /
Chemical Organic Carbon/ Reduced
substrate/ Waste
CO2 + H2O
Bio
cata
lytic
ano
de
Cat
hode
BioElectrochemical System (BES)
e- e-
H+
H+
H+
H+
CxHyOz → CO2 + H+ + e- MEC: H+ + e- → H2
Nutrients
Cell mass
Load/Power source
Reduction
DIRECT INDIRECT Redox biofilm matrix OM c-cyt Redox mediator
K. Rabaey, L. T. Angenent, U. Schroder, J. Keller, Bioelectrochemical Systems: From Extracellular Electron Transfer to Biotechnological Application, IWA Publishing, UK, 2010. B. E. Logan, D. Call, S. Cheng, H. V. M. Hamelers, T. Sleutels, A. W. Jeremiasse, R. A. Rozendal, Environ. Sci. Technol. 2008, 42, 8630. Borole AP, Reguera G, Ringeisen B, Wang Z, Feng Y, Kim, BH, 2011, Energy Environ. Sci. (Review paper) Electroactive Biofilms: Current Status and Future Research Needs, 4:4813-4834
Type of Cathode Product BES substrate . MFC Oxygen Electricity MEC Protons Biohydrogen BES Acetate Ethanol/biofuel BES Oxygen→ Hydrogen peroxide BES Carbon dioxide → Electrofuels BES other/sunlight →Photo/biofuels
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MEC Supporting Tasks for Biorefinery Application
Produce bio-oil /characterize, analyze aqueous phase
Microbial electrolysis of pyrolysis aqueous Phase
Membrane separations Biocatalyst recovery and recycle
Microbial electrolysis of furanic and phenolic Substrates
Membrane process modules, supplies
Life cycle analysis Techno-economic Analysis
Electrolysis cell materials
Understanding of biooil composition P
robl
em
Biooil pH, instability GHG
reduction
Solut
ions
Industry partners
Develop oil-water Separation methods
Loss of carbon via aqueous phase
Hydrogen requirement
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Potential for MECs in Algal Conversion Pathways
Without MECs
With MECs Sustainability, Special Issue: Sustainability in Bioenergy Production, Borole, A. P., 2015, Sustainable and Efficient Pathways for Bioenergy Recovery from Low-value Process Streams via Bioelectrochemical Systems in Biorefineries." 7(9): 11713-11726.
NREL/TP-5100-62368, 2014. Process Design and Economics for the Conversion of Algal Biomass to Biofuels: Algal Biomass Fractionation to Lipid- and Carbohydrate-Derived Fuel Products, R. Davis, et al.
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Future Work
• Achieve performance to enable commercial consideration
• Scale up studies
US Patent 7,695,834, April 2010. Borole, AP. Microbial fuel cell with improved anode.
Acknowledgements BioEnergy Technologies Office (CHASE Program) ORNL LDRD Program Oak Ridge National Laboratory Costas Tsouris, Ramesh Bhave RK Goud UTK Bredesen Center Alex Lewis University of Tennessee Institute of Agriculture Niki Labbe, Philip Ye, P. Kim, S. Ren Georgia Institute of Techology S. Pavlostathis, S. Yiacoumi S. Zeng, L. Park Industry Partners: The FuelCellStore, Inc. OmniTech International Pall Corporation
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Environ Sci Technol Conversion of residual organics in corn stover-derived biorefinery stream to bioenergy via microbial fuel cells. 47(1): 642-648. Borole, A. P., C. Hamilton, et al. (2013).