![Continuous high yield hydrogen gas production coupling system:
Dark fermenter → Microbial electrolysis cell
H2 H2
Dark
fermentation
Microbial
electrolysis
Any substrate Organic acids
(acetate,…)
BioH2 2013, August 5th-7th, Montréal, Canada
Outlet
Saline media
pH [7-8]](https://image.slidesharecdn.com/id-2318471-carmonatrablyfinal-141016120020-conversion-gate02/85/BioH2Conference-Alessandro-Carmona-2-320.jpg)
![MEC performances in comparison to other MEC studies
BioH2 2013, August 5th-7th, Montréal, Canada
Eapp./
V
Anode
material
T/
C
VMEC/
L
IA/
A m-2
Iv/
A m-3
Q/
L d-1
CE/ % YH2/
mol mol-1
QH2 /
m3 m-3 d-1
H2/
%
HRT/
h
Ref.
+0.2 Graphite
felt
37 4.00 2-3 400 7.5 22 2.28 0.15 ~90 12 This
work
-0.2 Graphite
brush
30 0.03 0.02 147 0.03 81 N.F. 3.6 68 24 [1]
+0.9 Graphite
brush
30 2.50 1.18 74 2.5 ˃100 N.F. 0.53 70 24 [2]
+0.8 Graphite
felt
28 0.20 2.91 40 N.F. 52 2.1 0.05 96.6 N.F. [3]
+1.5 Graphite
fiber
32 0.13 N.F. 1630 0.46 ˃100 2.0 4.3 53 6.5 [4]
+1.0 Graphite
felt
30 0.28 16.4 732 7.2 60 N.F. 5.6 N.F. 48 [5]
+1.2 Graphite
felt
30 0.05 6.00 0.6 0.008 N.F. 3.36 5.4 N.F. 6 [6]
[1] Nam et al. 2011, [2] Rader et al. 2010, [3] Chae et al. 2008, [4] Lee et al. 2010, [5] Sleutels et al., 2009, [6] Hrapovic et al., 2010
Notes:
•All values are well in line with previous literature data
•However, just a very few studies have reported the coupling of dark fermentation and MEC technology
•So far, theMEC using acetate as a model metabolite shows a stable performance
•Not enough available information onMECs under saline conditions](https://image.slidesharecdn.com/id-2318471-carmonatrablyfinal-141016120020-conversion-gate02/85/BioH2Conference-Alessandro-Carmona-18-320.jpg)
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BioH2Conference, Alessandro Carmona
This document summarizes a study coupling a microbial electrolysis cell (MEC) to a dark fermentation reactor for continuous hydrogen production. A saline dark fermenter converted glucose into organic acids like acetate. The MEC was fed these metabolites and produced hydrogen gas at over 90% purity with a conversion rate of 2.28 moles of hydrogen per mole of acetate. Overall, the coupled system achieved 0.48 moles of hydrogen per mole of glucose initially fed to the dark fermenter and maintained stable performance over several weeks of continuous operation under saline conditions.
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BioH2Conference, Alessandro Carmona
- 1. Innovative continuous high-yieldhydrogen-producing system: Coupling a microbial electrolysis cell fed with resultant dead-end metabolites of a saline dark fermentation reactor Alessandro A. Carmona-Martínez, Eric Trably and Nicolas Bernet Laboratory of Environmental Biotechnology, Narbonne-France (eric.trably@supagro.inra.fr) BioH2 2013, August 5th-7th, Montréal, Canada
- 2. Continuous high yieldhydrogen gas production coupling system: Dark fermenter → Microbial electrolysis cell H2 H2 Dark fermentation Microbial electrolysis Any substrate Organic acids (acetate,…) BioH2 2013, August 5th-7th, Montréal, Canada Outlet Saline media pH [7-8]
- 3. Introduction BioH2 2013,August 5th-7th, Montréal, Canada
- 4. Biological treatment ofsaline wastewaters Industries generating saline effluents: 5% of worldwide effluents!!! BioH2 2013, August 5th-7th, Montréal, Canada ↑ Organic matter! ↑ Salt! Lefebvre, O. et al, Water Res. 2006. 40: p. 3671-3682; Xiao, Y. et al, Environ. Technol. 2010. 31 (8-9): p. 1025-1043
- 5. Biological treatment ofsaline wastewaters BioH2 2013, August 5th-7th, Montréal, Canada Na+ Na+ Na+ Na+ 1,0 0,8 0,6 0,4 0,2 Pierra, M. et al, Int. J. Hydrogen Energy. 2013. (Revised version in submission) Na+ Na+ Na+ Na+ 0,0 9 19 29 38 48 58 75 H2max (molH2 molGLC-1) salinity (gNaClL-1) ■ Lactate ■ Ethanol ■ Propionate ■ Formate ■ Acetate ■ Butyrate Salt factory sediments pH8 Vibrio spp. Hydrogen yield Metabolite pattern
- 6. Overview of bioelectrochemicalsystems Configuration of a BES: membrane specificity, type of catalysts at both electrodes, and the source of the reducing power Harnisch, F. et al., ChemSusChem. 2009. 2(10): p. 921-926; Franks, A.E. et al., Biofuels. 2010. 184): p. 589-604; Logan, B.E. et al., Environ. Sci. Technol. 2008. 42(23): p. 8630-8640 Power supply or or Renewable energy Reducing power Anode Cathode Product Product BioH2 2013, August 5th-7th, Montréal, Canada Anode Cathode C+ A-e- e- C+ A-A-C+ C+ A-or or no membrane cation anion exchange membrane e- Microbially catalysed CO2 Organics Chemially or catalysed O2 H2O H+ H2 e- Electron acceptor Microbially catalysed Chemially catalysed or Electron acceptor Power production Short circuit e- e-e-e- e-e- e- Membrane 2 Rabaey, K. et al, Nat. Rev. Micro. 2010. 8(10): p. 706-716 „electrochemical device that exploits living microbial cells for the bioelectrocatalysis of anodic-oxidation and/or cathodic-reduction reactions“ Harnisch F. et al. Chem. Asian J. 2012, 7, 466 – 475
- 7. Objective of thestudy: coupling a microbial electrolysis cell fed with dead-end metabolites of a saline dark fermentation reactor BioH2 2013, August 5th-7th, Montréal, Canada
- 8. Materials & Methods BioH2 2013, August 5th-7th, Montréal, Canada
- 9. Dark fermenter 10 9 8 7 6 5 4 3 2 1 10 9 8 7 6 5 4 3 2 1 10 9 8 7 6 5 4 3 2 1 10 9 8 7 6 5 4 3 2 1 BioH2 2013, August 5th-7th, Montréal, Canada Agitation H2 1 M NaOH addition 3.5 % NaCl Glucose pH 7 Pump inlet pH meter Level Vw ~ 2 L pH control Jacket 37°C Adapted from Aceves-Lara, C. et al, Int. J. Hydrogen Energy. 2010. 35: p. 10710-10718 Pump outlet HRT~ 6 h To MEC Sediment as inoculum 0 0 20 18 16 14 12 10 8 6 4 2 0 0 20 18 16 14 12 10 8 6 4 2 0 0 YH2: 0.47 ± 0.06 molH2/molGlucose
- 10. BES: cross section 3.5 % NaCl Pump inlet BioH2 2013, August 5th-7th, Montréal, Canada AEM Cathode or CE Level Vw ~ 4 L Medium outlet Jacket 37°C Anode or WE Graphite Electrons H2 Carbon felt Projected: 750 cm2 254SMO 560 cm2 RE HRT~ 12 h Acetate pH 7
- 11. Biogas collector fromcathode Biogas collector from anode ~ 0.0 L Operation conditions: V: 4 L Q: 7.5 L/d HRT: ~12 h Starkey medium Acetic acid: 1.2 g/L*d (20 mM) pH 7 Port for biogas sampling Automatic volumeter for continuous biogas measurement Water bath at 37°C
- 12. Results & discussion BioH2 2013, August 5th-7th, Montréal, Canada
- 13. 20 mM 01 2 3 15 mM BioH2 2013, August 5th-7th, Montréal, Canada 10 mM 0 1 2 3 4 5 4 3 2 1 0 0 1 2 3 4 5 6 Chronoamperometric cycle duration/ days j/ A m-2 Bioelectrochemical biofilm development: an essential prerequisite for sustainable MEC performance Biofilmgrowth at an applied potential of +200 mV vs. SCE 1st CA batch cycle 2nd CA batch cycle 3rd CA batch cycle ←Substrate+ 10%Sediments ←Substrate+ 10%Sediments ←Substrate+ 10%Sediments Notes: Succesful strategy for the growth of biofilms derived fromsediments and acetate as carbon source Electroactive biofilms commonly ignored in MEC studies
- 14. Daily gas productionand composition in the continuous MEC BioH2 2013, August 5th-7th, Montréal, Canada
- 15. Mid-term continuous operationof pilot MEC Characterization of MEC during continuous feeding: Continuous hydrogen production with a composition higher than 90 % Performance stability for an MEC under halophilic conditions: 3.5 % NaCl BioH2 2013, August 5th-7th, Montréal, Canada
- 16. Concentration dependency test:“proof of attached biofilm” BioH2 2013, August 5th-7th, Montréal, Canada
- 17. MEC performances BioH22013, August 5th-7th, Montréal, Canada
- 18. MEC performances incomparison to other MEC studies BioH2 2013, August 5th-7th, Montréal, Canada Eapp./ V Anode material T/ C VMEC/ L IA/ A m-2 Iv/ A m-3 Q/ L d-1 CE/ % YH2/ mol mol-1 QH2 / m3 m-3 d-1 H2/ % HRT/ h Ref. +0.2 Graphite felt 37 4.00 2-3 400 7.5 22 2.28 0.15 ~90 12 This work -0.2 Graphite brush 30 0.03 0.02 147 0.03 81 N.F. 3.6 68 24 [1] +0.9 Graphite brush 30 2.50 1.18 74 2.5 ˃100 N.F. 0.53 70 24 [2] +0.8 Graphite felt 28 0.20 2.91 40 N.F. 52 2.1 0.05 96.6 N.F. [3] +1.5 Graphite fiber 32 0.13 N.F. 1630 0.46 ˃100 2.0 4.3 53 6.5 [4] +1.0 Graphite felt 30 0.28 16.4 732 7.2 60 N.F. 5.6 N.F. 48 [5] +1.2 Graphite felt 30 0.05 6.00 0.6 0.008 N.F. 3.36 5.4 N.F. 6 [6] [1] Nam et al. 2011, [2] Rader et al. 2010, [3] Chae et al. 2008, [4] Lee et al. 2010, [5] Sleutels et al., 2009, [6] Hrapovic et al., 2010 Notes: •All values are well in line with previous literature data •However, just a very few studies have reported the coupling of dark fermentation and MEC technology •So far, theMEC using acetate as a model metabolite shows a stable performance •Not enough available information onMECs under saline conditions
- 19. Microbial community structurethrough CE-SSCP 90 d Biofilm sample (bs1) Sediment as inoculum Electroactive biofilm High simplification of microbial diversity in the electroactive biofilm Microbial structure composed of a few abundant electroactive bacterial species *Thanks to Caroline Rivalland for SSCP analysis 90 d bs2 bs3 bs4 bs5 bs6 bs1 = bs2 … = bs6 BioH2 2013, August 5th-7th, Montréal, Canada
- 20. Conclusions BioH2 2013,August 5th-7th, Montréal, Canada
- 21. Overall production ofhydrogen H2 3.5 % NaCl Glucose pH 7 1.00 mol glucose 0.48 ± 0.08 mol H2 0.49 ± 0.21 mol lactate 0.49 ± 0.19 mol acetate 0.41 ± 0.04 mol ethanol 0.11 ± 0.08 mol butyrate Pump inlet HRT~ 6 h 2.28 ± 0.18 mol H2 mol acetate 1. Dark fermenter * Successful running under saline conditions 2. MEC H2 * Successful long-term running - no CH4 * High % H2 * High conversion yields + H2? Rivalland, C. et al, In preparation. BioH2 2013, August 5th-7th, Montréal, Canada
- 22. Thank you foryour kind attention…
Editor's Notes
- #6 Sad bacteria: http://www.clipartof.com/gallery/clipart/germ.html
- #7 In BESs, a plenitude of possible applications can be found (Fig. 1-6), from the original and promising production of electricity (Logan, et al., 2006), to hydrogen as a clean fuel (Logan, et al., 2008) and the production of useful chemicals (Rabaey and Rozendal, 2010) such as hydrogen peroxide, extraordinarily from wastewater (Fu, et al., 2010, You , et al., 2010). Nonetheless, the cited applications in this section would not be possible without the basic research on the microbe-electrode interactions which inexorably turn out to contribute to the betterment of the overall performance of this kind of systems by eliminating (or at least diminishing) electrochemical losses of BESs (Schröder and Harnisch, 2010). Therefore, the analysis of the microbe-electrode interactions would lead not only to a higher comprehension on improving the overall performance of BESs (see section 1.5) from the power production point of view but also on improving a more precise electron uptake by microorganisms for the production of useful and industrial demanded biochemicals (Nevin, et al., 2010, Ross, et al., 2011). As shown in Fig. 1-6, microbial-electrode interactions can take place in both electrode chambers depending on the application for which the BES has been designed. A simplified version of a BES system as shown in the insert of Fig. 1-6 is a potentiostatic controlled electrochemical half-cell in which an anode and a cathode are hosted within one vessel (LaBelle, et al., 2010). This experimental approach assures similar biological and environmental conditions for both electrodes and increases the reproducibility of the experiment by maintaining one of the electrodes at a constant potential permanently controlled against a reference electrode (e.g., vs. Ag/AgCl) (Bard, et al., 2008). This type of BES (with multiple modifications) is the one that has been extensively used in this Thesis.