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

8SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann

Bacterial H2 production (Clostridium)

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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

13SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann

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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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Glucose Hydrogène

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Bacterial H2 production (Clostridium)

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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

23SFGP 2011 Lille 29 nov. – 1er déc. 2011 – Biohydrogène : Etat de l’Art - S. Hiligsmann