Investigation of anaerobic digestion in a two-stage bioprocess producing hydrogen and methane

Transcription

1 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 1 15 th European biosolids and organic resources Leeds th nov Investigation of anaerobic digestion in a two-stage bioprocess producing hydrogen and methane Serge Hiligsmann, Christopher Hamilton, Laurent Beckers, Julien Masset, Philippe Thonart Walloon Centre of Industrial Biology, University of Liege, Belgium

2 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 2 Why? a two-stage anaerobic digestion H 2 + CH 4 Improve the AD process / integration in agro-food industries Resistance to shock loading (not a new topic : Pohland 1971) Rapid production of fuel (acidogenesis faster than methanogenesis) Higher energetic yields depending on substrates, process, Diversity of energetic fuels Energy density : ED H2 = 33 kwh/kg H 2 = 2.4 ED CH4 Combustion : H 2 + ½ O 2 H 2 O CO 2 = Ø Potential use in fuel cells : Yields FC > Yields engine

3 15th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 3

4 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 4 Introduction Processes for hydrogen production Microbial hydrogen production Two-stage anaerobic digestion Advancements in biohydrogen production Microbiology biochemistry - physiology Bioreactors Researches in University of Liege

5 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 5 Hydrogen production Methane steam reforming (200 C) CH 4 + H 2 O CO + 3H 2 CO + H 2 O CO 2 + H 2 Partial hydrocarbons oxydation 95 % of H 2 industrial production Coal or biomass gasification (High dry matter) C a H b O g + O 2 + H 2 O CO 2 + H 2 Water electrolyse H 2 O + ½ O 2 + H 2 Microbial production

6 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 6 Microbial hydrogen production Clostridium, Ruminococcus, Aeromonas, Bacillus, Escherichia, Chlorobium, Rhodospirullum, Chromatium,... Microorganisms : Bacteria Algae phototrophic chemotrophic

7 Carbone Source Light Anaerobiosis, Nutrients Carbone Source C 6 H 12 O 6 C 6 H 12 O 6 Phototrophic microorganisms Chemotrophic microorganisms CO 2 + H 2 Alcohols, acids,... in aqueous solution... 6CO H 2 High yields... 2CH 3 COOH + 2CO 2 + 4H 2 High production rate 15th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. 7

8 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. 8 Biodegradation processes Hydrolysis cellulases, amylases proteases, lipases, Acidogenesis Bacillus, Enterobactéria, Acetogenesis Clostridium, Ruminococcus, COMPLEX ORGANIC MATTER SOLUBLE ORGANIC COMPOUNDS (Carbohydrates, amino acids, fatty acids) VOLATILE FATTY ACIDS ALCOHOLS ACETIC ACID CO 2, H 2 Methanogenesis Methanobacter, Methanosarcina, CH 4 CO 2

9 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 9 Bacterial H 2 production (Clostridium) Concentration (mm) Time (h) Temps (heure) Volume d'hydrogène par gramme de glucose consommé (ml H2/g glucose) Hydrogen production yield (ml/g glucose) Glucose Succinate Lactate Formiate Acétate Ethanol Butyrate Hydrogène

10 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 10 Facultative / strict anaerobes Citrobacter freundii Clostridium butyricum Hydrogen production yield (ml/g glucose) Conversion yields - Enterobacteria : 0,8 mole H 2 /mole glucose - Clostridia : 2,5 mole H 2 /mole glucose Production rate : 6 25 m³ H 2 / m³. day (classic AD : 0,3 6 m³ CH 4 / m³.d)

11 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 11 Diversity of carbohydrates substrates Clostridium butyricum Hydrogen production yield (ml/g COD) Glucose Maltose Lactose Starch Sucrose Clostridium butyricum

12 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 12 Dark Fermentation more adapted for industrial H 2 production from wastewater and biomass pollution reduction, energy generation 70 to 250 m³ H 2 / ton of COD 3 to 12 m³ H 2 per day per m³ of bioreactor liquid or solid wastes containing carbohydrates (starch, sucrose, lactose, ) followed by effective methanisation

13 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 13 Brewery effluents m 3 /d wastewaters 1400 mg/l DBO 5 Residual organic matter CO 2 + H m 3 H kw Biogas treatment Fuel cell 150 kw 225 kw + hot water Bioreactor I CO 2 + CH 4 Engine or steam power 1000 kw 750 kw Steam and mechanic energy Bioreactor II Ultimate treatment Natural environment

14 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 14 Advancements in biohydrogen production Strain selection Optimisation of culture conditions Optimisation of bioreactors Researches in University of Liege

15 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 15 Strain selection H 2 production yield (ml/g glucose) AD sludge Clostridium but. Citrobacter f. Improvement of H 2 production by mixed cultures selection of spore-forming bacteria thermal, acidic or alkaline treatment

16 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 16 Optimisation of culture conditions H 2 production yield (ml/g glucose) Clostridium butyricum CWBI1009

17 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 17 Optimisation of metabolic pathways Acetate : C 6 H 12 O H 2 O 2 CH 3 COOH + 4 H CO 2 Butyrate : C 6 H 12 O 6 CH 3 CH 2 CH 2 COOH + 2 H CO 2

18 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 18 Optimisation of bioreactor 2.3 L Sequenced batch mode Formate Acetate Ethanol Butyrate Lactate H 2 yield H 2 production rate Clostridium butyricum CWBI1009 substrate converted through specific metabolic pathways with maximum H 2 yields

19 Optimisation of bioreactor UASB sludge themally treated (80 C, 30 min) H 2 yields (200 to 260 ml H 2 /g COD) lower than with pure strains 15 th European instability biosolids of microbial and organic populations resources, Leeds, need Nov. for further 2010 : investigations Two-stage anaerobic digestion S. Hiligsmann 19

20 Bacterial H 2 production (Clostridium) Time Temps (h) Temps (heure) (heure) Concentration (mm) Volume d'hydrogène par gramme de glucose Hydrogen consommé ml production H2/g glucose (ml (ml/g H2/g - ml glucose) glucose) H2/h Glucose Succinate Lactate Glucose Formiate Hydrogène Acétate Ethanol Butyrate Hydrogène 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 20

21 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 21 Bacterial H 2 production (Clostridium) Concentration (mm) Time (h) Temps (heure) ml H2/g glucose - ml H2/h Glucose Hydrogène negative impact of H 2 partial pressure need for further investigations

22 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 22 Cumulative biogas production (l) Feasibility of 2 nd stage 20L Sequenced batch reactor Cumulative biogas production Biogas production rate 3,50 3,00 2,50 2,00 1,50 1,00 0,50 Biogas production rate (l/d) Time (d) 0,00 high efficiency of methanogenesis :170 ml CH 4 /g COD

23 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 23 CWBI researches and collaborations CWBI : strain selection, hydrogenases expression, bioreactor design (immobilisation, high G/L transfer, ), scale-up (up to 1 m³) Collaborations : biogas treatment, fuel cell developments (2-220 kw), hydrogenases characterisation, algal biohydrogen production Companies: industrial developments

24 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 24 Conclusions advantages of a two-stage anaerobic digestion process Resistance to shock loading, specific optimised conditions (ph, ), high yields and production rate, production of two fuels with specific interest H 2 + CH 4 biohydrogen production improved strain selection, ph, bioreactor, need for further investigations for optimatisation G/L transfer, stability of microbial populations (immobilisation, ), scale-up, compact bioreactors,

25 Thank you for your attention 15 th European biosolids and organic resources, Leeds, Nov : Two-stage anaerobic digestion S. Hiligsmann 25