SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
La production de biohydrogène à partir de substrats carbohydratés :
état de l'art
SFGP 2011Lille, 29 nov. – 1er déc. 2011
Serge Hiligsmann, Laurent Beckers, Julien Masset, Christopher Hamilton, Philippe Thonart
Walloon Centre of Industrial Biology, University of Liege , Belgium
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Introduction• Processes for hydrogen production• Microbial hydrogen production• Two-stage anaerobic digestion
Advancementsin biohydrogen production
• Microbiology – biochemistry - physiology• Bioreactors• Researches in University of Liege
2SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
3SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
– Water electrolyse
H2O + ½ O2 + H2
– Microbial production
– Methane steam reforming (800 °C)
CH4 + H2O CO + 3H2
CO + H2O CO2 + H2
– Partial hydrocarbons oxydation
– Coal or biomass gasification (High dry matter)
CaHbOg + O2 + H2O CO2 + H2
95 % of H
2 industrial production
(500 109 N
m³/year)
Hydrogen production
4SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Microbial hydrogen production
Clostridium, Ruminococcus, Aeromonas, Bacillus,Escherichia, Citrobacter, Chlorobium, Rhodospirullum,Chromatium, ...
Microorganisms :
• Bacteria• Algae
phototrophic
chemotrophic
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Phototrophic microorganisms
Light
Chemotrophicmicroorganisms
Anaerobiosis, Nutrients
CO2 + H2
... 6CO2 + 12H2
High yields
Alcohols, acids, ...in aqueous solution
... 2CH3COOH + 2CO2 + 4H2
High production rate
Carbone SourceC6H12O6 C6H12O6
Carbone Source
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
COMPLEX ORGANICMATTER
SOLUBLE ORGANIC COMPOUNDS
VOLATILE FATTY ACIDS ALCOHOLS
Hydrolysiscellulases, amylasesproteases, lipases, …
AcidogenesisBacillus, Enterobactéria, …
(Carbohydrates, amino acids, fatty acids)
AcetogenesisClostridium, Ruminococcus, …
ACETIC ACID
CO2 ,H2
MethanogenesisMethanobacter, Methanosarcina, …
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Biodegradation processes
CH4
CO2
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Why ? a two-stage anaerobic digestion H2 + CH4
• Resistance to shock loading (not a new topic : Pohland 1971)
• Rapid production of fuel (acidogenesis faster than methanogenesis)
• Higher energetic yields 10-30% depending on substrates, process, …
Improve the AD process / integration in agro-food industries
Diversity of energetic fuels
• Energy density : EDH2 = 33 kWh/kg H2 = 2.4 EDCH4
• Combustion : H2+ ½ O2 H2O CO2 = Ø• Potential use in fuel cells : YieldsFC > Yieldsengine
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Bacterial H2 production (Clostridium)
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Temps (heure)
Con
cent
ratio
n (m
M)
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Vol
ume
d'hy
drog
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par
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de g
luco
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cons
omm
é (m
l H2/
g gl
ucos
e)
Glucose Succinate Lactate Formiate Acétate Ethanol Butyrate Hydrogène
Time (h)
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Clostridium butyricum
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Glucose Maltose Lactose Starch Sucrose
Diversity of carbohydrates substrates
Clostridium butyricum
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Dark Fermentation
more adapted for industrial H2 production from wastewater and biomass
pollution reduction, energy generation
70 to 250 m³ H2/ ton of COD
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3 to 12 m³ H2 per day per m³ of bioreactor(classical AD : 0,3 – 6 m³ CH4/ m³.d)
substrates = liquid or solid wastes containing carbohydrates (starch, sucrose, lactose, …)
followed by effective methanisation
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Residual organicmatter
BioreactorI
BioreactorII
CO2 + H2Biogas
treatment Fuel cell
CO2 + CH4
Engine or steam power Steam and
mechanic energy
Ultimate treatment
Brewery effluents 10 000 m3/d wastewaters1400 mg/L DBO5
3000 m3 H2
375 kW150 kW
+ hot water
1000 kW
Naturalenvironment
225 kW
750 kW
12SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Advancementsin biohydrogen production
• Strain selection• Optimisation of culture conditions• Optimisation of bioreactors• Researches in University of Liege
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Strain selection
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AD sludge Clostridium but. Citrobacter f.
Improvement of H2 production by mixed cultures selection of spore-forming bacteria
thermal, acidic or alkaline treatment
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
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Strain selection
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
y = -56,004x4 + 1386,5x3 - 12756x2 + 51608x - 77225
R2 = 0,9951
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Optimisation of culture conditions
Clostridium butyricum CWBI1009
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
• Acetate :
C6H12O6 + 2 H2O → 2 CH3COOH + 4 H2 + 2 CO2
• Butyrate :
C6H12O6 → CH3CH2CH2COOH + 2 H2 + 2 CO2
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Optimisation of metabolic pathways
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Optimisation of bioreactor 2.3 L Sequenced batch mode
Lactate
Formate
Acetate
Ethanol
Butyrate
H2 yield
H2 production rate
substrate converted through specific metabolic pathways with maximum H2 yields
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Clostridium butyricum CWBI1009
Feasibility of 2nd stage20L Sequenced batch reactor
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high efficiency of methanogenesis :170 ml CH4 /g COD
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
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ml H
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Glucose Hydrogène
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1015
2025
3035
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Bacterial H2 production (Clostridium)
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n (m
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Vol
ume
d'hy
drog
ène
par
gram
me
de g
luco
se
cons
omm
é (m
l H2/
g gl
ucos
e)
Glucose Succinate Lactate Formiate Acétate Ethanol Butyrate Hydrogène
Time (h)
negative impact of H2 partial pressure need for further investigations
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
CWBI researches and collaborations
CWBI : strain selection, hydrogenases expression, bioreactor design (immobilisation, high G/L transfer, …), scale-up (up to 1 m³)
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Collaborations : biogas treatment, fuel cell developments (2-220 kW), hydrogenases characterisation, algal biohydrogen production
www.microh2.ulg.ac.be
Companies: industrial developments
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Conclusions
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advantages of a two-stage anaerobic digestion processResistance to shock loading, specific optimised conditions (pH, …), high yields and production rate, …
production of two fuels with specific interest H2 + CH4
biohydrogen production improved strain selection, pH, bioreactor, …
need for further investigations for optimatisationG/L transfer, stability of microbial populations (immobilisation, …), scale-up, compact bioreactors, …
SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann
Thank you for your attention
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