HYSYDAYS Turin 8th October 2009 PARAMETERS AFFECTING THE GROWTH AND HYDROGEN PRODUCTION OF THE GREEN ALGA CHLAMYDOMONAS REINHARDTII Bojan Tamburic Dr Fessehaye W. Zemichael Prof Geoffrey C. Maitland Dr Klaus Hellgardt CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design SOLAR HYDROGEN PROJECT Sunlight Water Hydrogen • Direct routes to solar H2 from water • Funded by EPSRC • Run by the Energy Futures Lab at Imperial College London Solar energy conversion efficiency Light Heat Wind Hydro Biomass Fossil Technological development Diversity of H2 supply: • • • • Steam methane reforming Coal/biomass gasification Electrolytic/photolytic processes Thermal/thermochemical processes SOLAR HYDROGEN PROJECT Hydrogen as a fuel: • Lightest (storage) • Most efficient (fuel cells) • Cleanest • Most available ... maybe Cleanest: • Must consider entire life cycle – including production • Requires a carbon-neutral, sustainable process (e.g. use sunlight) Most available: • Hydrogen found in hydrocarbons, carbohydrates and water • Water is the most plentiful and widespread resource Solar Hydrogen Project - direct routes to H2 from sunlight and water: • Photoelectrochemical • Biophotolytic CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design BIOPHOTOLYTIC H2 PRODUCTION - SCIENCE Unicellular green alga C.reinhardtii produces H2 under anaerobic conditions Merchant et al., 2007 Photosystem II protein complex splits water into oxygen, protons and electrons Hydrogenase enzyme facilitates proton and electron recombination to produce H2 – but it is inactivated in the presence of O2 Anaerobic conditions imposed by sulphur deprivation Melis, 2002 BIOPHOTOLYTIC H2 PRODUCTION - METHOD Algal growth • Tris-acetate phosphate (TAP) growth medium – Source of N, C, P, S and trace elements • Measured by: – Chlorophyll content – Optical density (OD) • Influenced by: – Light intensity and wavelength – Agitation and pH H2 measurement • Techniques: – – – – Water displacement Injection mass spectrometry Reversed Clark electrode Membrane inlet mass spectrometry (MIMS) • H2 production quantified in terms of: – Productivity – Yield – Photochemical efficiency (13% theoretical maximum, 2% attained) Sulphur deprivation • Causes metabolic changes in algae that induce anaerobic H2 production • TAP medium replaced by sulphurdeplete TAP-S medium by: – Centrifugation – Dilution – Ultra-filtration • Sulphur re-insertion required to prolong algal lifetime Photobioreactors • Types: – – – – Vertical column reactor Stirred-tank batch reactor Tubular flow reactor Flat plate reactor CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design C.REINHARDTII GROWTH KINETICS • C.reinhardtii grown in Aqua Medic® vertical column reactors • Agitation provided by bubbled air (or CO2) gas-lift system • 170 μEm-2s-1 PAR (18 Wm-2) of cool white light incident on culture • Room temperature Absorption spectrum: • Pigments extracted by acetone or methanol • Absorption maxima in the purple and red regions of visible spectrum – Carotenoids absorb in 400-500 nm range – Photosystem II absorption peak at 663 nm C.REINHARDTII GROWTH KINETICS • • • • C.reinhardtii reproduce by meiosis (cell splitting) Initial exponential growth Cell density limited by light penetration through culture causing saturation Logistic (sigmoid) growth kinetics Increase agitation rate: • Decrease growth rate • Increase maximum attainable OD Increase light intensity: • Increase growth rate and maximum attainable OD • What is the limit? CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design C.REINHARDTII H2 PRODUCTION KINETICS • • • • • C.reinhardtii produce H2 under anaerobic conditions Anaerobic conditions imposed by sulphur deprivation Sulphur deprivation induced by centrifugation or dilution H2 yield measured by water displacement H2 identified by injection mass spectrometry Stirred-tank batch reactor: • Mechanical agitation • Cool white light side-illumination • Centrifugation Sartorius® tubular flow reactor: • Peristaltic pump • Helix geometry illumination • Dilution C.REINHARDTII H2 PRODUCTION KINETICS Stirred-tank batch reactor (centrifugation) • 3 distinct phases: – Oxygen consumption – Hydrogen production – Cell death • H2 yield of 5.2±0.3 ml/l • Higher initial cell density • Brief start-up time Tubular flow reactor (dilution) • Continuous measurement of pO2, pH and OD • H2 yield of 3.1±0.3 ml/l • Photochemical efficiency of approximately 0.1% • Process easier to implement and scale up CONTENT • Solar Hydrogen Project • Biophotolytic H2 Production • C.reinhardtii Growth Kinetics • C.reinhardtii H2 Production Kinetics • Photobioreactor Design PHOTOBIOREACTOR DESIGN Flat plate reactor: • 1 litre system • Specifically constructed for H2 production • H2 detection by MIMS • Strong scale-up opportunity CONCLUSION • Solar Hydrogen Project – Clean and renewable H2 production – Integrated, cross-disciplinary approach to link green algal H2 production with engineering methods • Results – C.reinhardtii absorption peak at 663nm – Agitation rate and light intensity have significant effect on C.reinhardtii growth – H2 production by C.reinhardtii: • 5.2±0.3 ml/l in stirred-tank batch reactor following centrifugation • 3.1±0.3 ml/l in tubular flow reactor following dilution • Outlook – Improve H2 production efficiency – Advance photobioreactor design – H2 will become the sustainable fuel of the future Thank you for listening! Any questions? bojan.tamburic@imperial.ac.uk