integrated biological hydrogen production alan guwy · anaerobic digestion ... integrated...
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© University of South Wales
Integrated Biological
Hydrogen Production
Alan Guwy
University of South WalesSustainable Environment
Research Centre
H2FC SUPERGEN Conference
All-Energy AECC Aberdeen 21st May 2013
© University of South Wales
Hydrogen Energy Systems
Biohydrogen
Microbial Fuel Cells
Bioenergy Systems
Anaerobic Digestion
Waste Water Treatment
Environmental Analysis
Advanced Nanomaterials
© University of South Wales
Hydrogen Energy Systems
Biohydrogen
Microbial Fuel Cells
Bioenergy Systems
Anaerobic Digestion
Waste Water Treatment
Environmental Analysis
Advanced Nanomaterials
Dark-Biohydrogen Fermentation
• Applicable for co-product/waste streams food industry and to
energy crops
• Bacteria involved, particularly clostridia use the enzyme
hydrogenase
• Use carbohydrates: glucose, sucrose, starch, cellulose, hemi-
celluloses
• H2 yield depends on fermentation products and amount of
readily biodegradable carbohydrate
Dark fermentation - H2 yieldTheoretical:
Hexose CH3COOH (acetic acid) + 4 H2
(that is 4 mol H2/mol hexose or 0.5 m3 H2 / kg carbohydrate)
Hexose CH3CH2CH2COOH (butyric acid) + 2 H2
(that is 2 mol H2/mol hexose or 0.25 m3 H2 / kg carbohydrate)
• A mix of acetate and butyrate is usual with H2 yields approx. 1 to 2
mol H2/mol hexose utilised
Significant energy remains in acetate and butyrate
Reduced ProductsNaOH, Clean H2O
HOCl, H2O2 etc
H2 + CO2
e- + H+ + CO2
Hydrogen fermentation
Methanefermentation
Photo fermentation
MFC
MEC
CH4 + CO2
H2 + CO2
H2 + CO2Biomass
e-
BES e-
Integrated Biological Hydrogen Production Options
Guwy, A.J., Dinsdale, R.M., Kim, J.R., Massanet-Nicolau, J., Premier, G., 2011. Fermentative biohydrogen production systems integration. Bioresource Technology 102 (18), 8534–8542.Premier, G.C., Kim, J.R., Massanet-Nicolau, J., Kyazze, G., Esteves, S.R.R., Penumathsa, B.K.V., Rodríguez, J., Maddy, J., Dinsdale, R.M., Guwy, A.J., 2013. Integration of biohydrogen, biomethane and bioelectrochemical systems. Renewable Energy 49 (2013), 188–192.
Reduced ProductsNaOH, Clean H2O
HOCl, H2O2 etc
H2 + CO2
e- + H+ + CO2
Hydrogen fermentation
Methanefermentation
Photo fermentation
MFC
MEC
CH4 + CO2
H2 + CO2
H2 + CO2Biomass
e-
BES e-
Hydrogen-Methane Fermentation
Guwy, A.J., Dinsdale, R.M., Kim, J.R., Massanet-Nicolau, J., Premier, G., 2011. Fermentative biohydrogen production systems integration. Bioresource Technology 102 (18), 8534–8542.Premier, G.C., Kim, J.R., Massanet-Nicolau, J., Kyazze, G., Esteves, S.R.R., Penumathsa, B.K.V., Rodríguez, J., Maddy, J., Dinsdale, R.M., Guwy, A.J., 2013. Integration of biohydrogen, biomethane and bioelectrochemical systems. Renewable Energy 49 (2013), 188–192.
Biohydrogen Production in an Integrated Anaerobic system-( dark fermentation)
Fermentation
End Products
Optimised Methanogenic
Stage
Optimised Methanogenic
Stage Methane Reactor
CH4+CO2
Biomass feedstock
Hydrogen Reactor
Advanced water recycling
Soil Conditioner
H2+CO2
33% conversion 90% energy conversion (substrate)
CH4+H2
pH=5.2 pH=7.0
SERC: Bio-H2/Bio-CH4
Year Authors Research Results
2000 Mizuno et al Glucose Continuous H2
2005 Hussy et al Sucrose and sugar beet Continuous H2
2007 Hawkes et alFlour milling co-product
(Batch) Batch H2
Kyazze et al Fodder maize Continuous H2
2010 Massanet-Nicolau et al Sewage Biosolids Continuous 2 stage H2 + CH4
2012 Massanet-Nicolau et al Wheat feed pellets Continuous 2 stage H2 + CH4
Direct fermentation of complex substrates to H2
• Perennial rye grass (21.8 ± 8 cm3 H2 /g dry matter)
• Fructo-oligosaccharides (218 ± 28 cm3 H2 /g chicory )
• Fodder maize (62.4 ± 6.1 cm3 H2/g dry matter)
• However, most of the insoluble polymeric components remains unutilised
– pre-treatment could improve further the energy recovered
•Manually fed continuous operation
•15 hour HRT
•10 litre bioreactor inoculate with anaerobes in sewage sludge
•pH 5.5 and 35oC
• Lab trials showed that 64m3 H2 + potentially 244m3 CH4 could be produced from 1 tonne wheatfeed (20% v/v H2 and 80% CH4)
Hydrogen Production from Wheat Feed
Hawkes F R, Forsey H, Premier G C, Dinsdale, R M, Hawkes D L, Guwy A J, Maddy J, Cherryman S, Shine J and Auty D. (2008). Fermentative Hydrogen Production froma Wheat Flour Industry Co-product. Bioresource Technology. 99 5020–5029
Biohydrogen Pilot Scale
R&D scaling up to pilot scale
•Industrial systems
•Energy balance
•System control & optimistion
Pilot scale biohydrogen and biogas plant using wheatfeed
Pilot scale biohydrogen & biomethane plant at IBERS Aberystwyth using rotated crops
H2 reactor 1.25m3
CH4 reactor 10m3
GHG Saving
•1.4 t CO2 eq t-1
carbon saving
Bio-H2/Bio-CH4
Lab Scale:
CH4 Bioreactor
H2 Bioreactor
Comparison of single BioCH4 with Two stage BioH2/BioCH4
Feed
H2
CH4
CH4
CH4
18h
20d
11.25d
19.25d
Single Stage20d HRT
Two Stage12d HRT
Two Stage20d HRT
Substrate: Wheat feed
Pretreatment: 24 h @ pH 11
Hydrogen reactor pH: 5.5
Methane reactor pH: 7.0
Temperature: 35oC
Massanet-Nicolau et al., Bioresource Technology, (2013) 129 pp. 561-567.
Hydrogen Production
Pro
duction R
ate
(cm
3m
in-1
)
Time (Days)
Yie
ld (
L k
g-1
VS
Fed)
0
5
10
15
0
4
8
12
0 10 20 30
Production rate (cm3 min-1)
Yield (L Kg-1 VS)
Production Rate
Yield
Massanet-Nicolau et al., Bioresource Technology, (2013) 129 pp. 561-567.
Increased methane production when coupled with biohydrogen reactor
0
150
300
450
0
10
20
30
0 10 20 30
Production RateYield
Pro
du
ctio
n R
ate
(cm
3m
in-1
)
Yiel
d (
L kg
-1V
S Fe
d)
Time (Days)
0
150
300
450
0
10
20
30
0 10 20 30
0
150
300
450
0
10
20
30
0 10 20 30
0
150
300
450
0
10
20
30
0 10 20 30
1 stage – 20 day HRT 2 stage – 12 day HRT 2 stage – 20 day HRT
Feedstock
Effluent
(Reduction percentages are in parentheses)
Single-stage
20 day HRT
Two-stage
12 day HRT
Two-stage
20 day HRT
CH4 Yield 261.14 306.09 (17.5) 359.65 (37.7)
Volatile Solids (g L-1) 48.02 15.97 (66.7) 15.9 (66.9) 13.56 (71.8)
COD (g L-1) 58.61 21.65 (63.1) 22.76 (61.2) 18.49 (68.5)
Carbohydrate (g L-1) 26.24 3.37 (87.2) 5.58 (78.7) 4.6 (82.5)
VFA (mg L-1) 572 287 237 243
Massanet-Nicolau et al., Bioresource Technology, (2013) 129 pp. 561-567.
Energy Yields
0
2
4
6
8
10
12
14
Single stage20 day
Two Stage12 day
Two Stage20 day
Ener
gy y
ield
fro
m b
ioga
s(M
J kg
-1V
S)
8.73
10.30
(+17.9%)
10.30
(+38.5%)
• 38% increase in energy yields
• 18% increase in energy yields even when reducing residence time
• Relatively small difference in VS reduction between single and two stage digestion
Massanet-Nicolau et al., Bioresource Technology, (2013) 129 pp. 561-567.
Further Work - Molecular
The next phase of research:
• Identifying the microbial differences between single stage CH4 and two stage H2/CH4 fermenters using a variety of substrates
• Quantifying these differences using molecular tools such as pyrosequencing
Biogas
Fischer-
Tropsch
Synthesis and
Separation
Steam Reforming:
Syngas
Gas
Engine
PEMFC
< 10 ppm CO
70-90 C
MeOH / DME
synthesis
MeOH
Water Gas Shift and
CO2 Removal: H2
SOFC
500-1000 C
Gas Clean-up /
Desulfurisation
CO2 Removal:
biomethane
Biogas Utilisation Options
DC and Heat
DC
Using Biogas from BioH2/BioCH4
i-V Plot of SOFC
operating at 850°C on
•H2 (2 cm3 min-1)
•and simulated biogas
(CH4:CO2 1:0.5 cm3 min-1)
Similar power output for hydrogen and simulated biogas
Laycock et al., Dalton Transactions, 2011 40 (20), pp. 5494-5504,.
Reduced ProductsNaOH, Clean H2O
HOCl, H2O2 etc
H2 + CO2
e- + H+ + CO2
Hydrogen fermentation
Methanefermentation
Photo fermentation
MFC
MEC
CH4 + CO2
H2 + CO2
H2 + CO2Biomass
e-
BES e-
Hydrogen fermentation -Microbial Electrolysis Cells (MEC)
Guwy et al. Bioresource Technology 2011
Dark fermentation BioH2/Microbial Electrolysis Cells (MEC)
H2+CO2+
H2reactor
MEC
H2+CO2
To Land
Acetate
Biomass
Remove CO2
PEMFC
Fermentation + microbial catalysed electrolysis
C6H12O6 + 2H2O 2CH3COOH + 2CO2 + 4H2
CH3COOH + 2H2O 2CO2 + 4H2
Using
Acetate
Theoretically
12 mol H2 / mol
BiofilmElectrode
Microorganisms
e-
e-
e-
e-
H2
H+
H+
H+H+
Membrane
2HCO3-
H2H2
H2
H2Anode Cathode
Microbial Electrolysis - Functionality
Acetate & ButyrateFrom dark fermentation
Vapplied 118 mV (lower than water electrolysis = 1230 mV (pH7))
Challenges for MECs
• Low CE (substrate to electrons)• Competing biological pathways-Methanogenesis• Maximise substrate availability to biofilm• Utilisation of both acetate and butyrate from dark
biohydrogen fermentation stage• Substrate migration to cathode
• Poor cathodic H2 efficiency (electrons to H2)• H2 diffusion to anode (worse at low current densities)• Efficient evolution of hydrogen from the cathode
chamber
25
Monolithic carbon foam
electrode
•Increasing flowrate
•Not much mixing
•Shear does exist
Carbon fiber veil and former
•Increasing flowrate
•Better mixing with velocity
mW
Flowrate
3D arrow plots showing fluid particle velocities (with arrows showing velocity field direction and their tone indicates magnitude); zoomed in on helical flow path MMCC (a) – (c); and LVSF (a) – (c). Inlet velocities and flow rates:
(a, d) Vin = 1.67e-9 m3 s-1 [0.1 mL min-1], (b, e) 3.33e-8 m3 s-1 [2 mL min-1], (c, f) 1.25e-7 m3 s-1 [7.5 mL min-1].
Kim J.R., Boghani H.C., Amini N., Aguey-Zinsou K.-F., Michie I., Dinsdale R.M., Guwy A.J., Guo Z.X. and Premier G.C.,. Journal of Power Sources, 213, 382-390 (2012).
Anode Systems for Tubular Microbial Fuel Cells (MFC)
Kim, J.R., J. Rodríguez, F.R. Hawkes, R.M. Dinsdale, A.J. Guwy, G.C. Premier. 2011. Increasing power recovery and organic removal efficiency using extended longitudinal tubular microbial fuel cell (MFC) reactors. Energy and Environmental Sciences. Energy & Environmental Science. 4(2): 459 – 465.
Ion exchange Membrane
Cathode
Hydrogel
Plastic tube shell
Anode
Flow path
Tubular MEC Design
Outer cathode chamber
Inner anode chamber
Anion
exchange
membrane
(orange)
Cathode
sleeve
(white)
Anode
chamber
(black)(a) Tubular microbial electrolysis cell schematic, (b) drawing of cathode and anode chamber assembly and (c) anode chamber membrane and cathode sleeve assembly
(a)
(b) (c)
Kyazze, G., Popov, A., Dinsdale, R., Esteves, S., Hawkes, F., Premier, G., Guwy, A. (2010). Influence of catholyte pH and temperature on hydrogen
production from acetate using a two chamber concentric tubular microbial electrolysis cell. International Journal of Hydrogen Energy, 35 (15) 7716-7722.
Summary
29
• Fermentative hydrogen production can be integrated with biomethane systems to increase energy recovery.
• Acetate and butyrate co-products can be utilised in microbial electrolysis cells for increased hydrogen production.
• Further work is needed for BioH2/MEC systems to out compete BioH2/bioCH4 systems.
Acknowledgements
30
ERDF H2 Wales projectEPSRC SUPERGEN SHEC projects
EP/H019480/1 and EP/E040071/1.
Alan GuwySustainable Environment Research Centre
University of South [email protected]