0 Bewertungen0% fanden dieses Dokument nützlich (0 Abstimmungen)
19 Ansichten38 Seiten
Photosynthesis drives a carbon cycle that is 1 to 2 orders of magnitude greater than the fossil C cycle. Microalgae have been studied for over 50 years as potential sources of foods, feeds, fertilizers and fuels. A 200,000 ton anaerobic bioreactor landfill has been built in northern California. This TALK ADDRESSES the HOPE and the HYPE.
Photosynthesis drives a carbon cycle that is 1 to 2 orders of magnitude greater than the fossil C cycle. Microalgae have been studied for over 50 years as potential sources of foods, feeds, fertilizers and fuels. A 200,000 ton anaerobic bioreactor landfill has been built in northern California. This TALK ADDRESSES the HOPE and the HYPE.
Photosynthesis drives a carbon cycle that is 1 to 2 orders of magnitude greater than the fossil C cycle. Microalgae have been studied for over 50 years as potential sources of foods, feeds, fertilizers and fuels. A 200,000 ton anaerobic bioreactor landfill has been built in northern California. This TALK ADDRESSES the HOPE and the HYPE.
April 27, 2004, Alumni Center, Stanford University Biomass Energy GCEP Energy Workshop April 27, 2004, Alumni Center, Stanford University Biomass Energy Photosynthesis, Algae, CO 2 and Bio-Hydrogen John R. Benemann Institute for Environmental Management, Inc. (Not for profit) Palo Alto and Walnut Creek, California jbenemann@aol.com 2 3 200,000 ton Anaerobic Bioreactor Landfill Davis, N. California (IEM, Inc. and Yolo County, 2004) 200,000 ton Anaerobic Bioreactor Landfill Davis, N. California (IEM, Inc. and Yolo County, 2004) 4 Photosynthesis, Microalgae and H 2 Production Photosynthesis, Microalgae and H 2 Production Photosynthesis drives a carbon cycle that is 1 to 2 orders of magnitude greater than the fossil C cycle. Microalgae have been studied for over 50 years as potential sources of foods, feeds, fertilizers and fuels, based in large part on their reputed ability to efficiently convert solar energy into chemical energy, either CO2 into biomass or even directly into hydrogen. THIS TALK ADDRESSES THE HOPE AND THE HYPE. 5 6 Light-induced electron-transfer steps in PS II (Red arrows: when the central pigments are excited by light they share the excitation (Science, March 04) Light-induced electron-transfer steps in PS II (Red arrows: when the central pigments are excited by light they share the excitation (Science, March 04) Water Splitting and O2 producing Mn Center 7 Bessel Kok, 1973 Bessel Kok, 1973 8 Effect of high light intensity on pigment Content Effect of high light intensity on pigment Content Dunaliella salina High Light on left (yellow) Low Light on right (green) 9 f f . From Neidhardt, Benemann and Melis, 1998 10 -20 0 20 40 60 80 100 0 400 800 1200 1600 2000 2400 2800 3200 Light-saturation Curves of Photosynthesis Light-saturation Curves of Photosynthesis O x y g e n
e v o l u t i o n m m o l O 2 ( m o l
C h l ) - 1 S - 1 WT Chl def. Chl b-less Chlamydomonas reinhardtii Mutants, Dr. J . Polle, Brooklyn College Light Intensity, E m-2 s-1 11 Next Step: Outdoor Testing Dr. J. C. Weisaman, SeaAg, Inc. Vero Beach, FL Next Step: Outdoor Testing Dr. J. C. Weisaman, SeaAg, Inc. Vero Beach, FL WT Mutant CM2 Generation mutants of strains that can grow outdoors (Prof. Polle) Diatom Cyclotella 12 13 MICROALGAE R&D PONDS IN ROSSWEL, NEW MEXICO MICROALGAE R&D PONDS IN ROSSWEL, NEW MEXICO 14 Typical High Rate Pond Design Typical High Rate Pond Design 15 Microalgae Production Plant in Hawaii (Cyanotech Corp). Red ponds for Haematococcus production, others cultivate the cyanobacterium Spirulina (known to produce H2 and candidate for indirect biophotolysis process) Microalgae Production Plant in Hawaii (Cyanotech Corp). Red ponds for Haematococcus production, others cultivate the cyanobacterium Spirulina (known to produce H2 and candidate for indirect biophotolysis process) 16 International Network on Biofixation of CO2 and Greenhouse Gas abatement with Microalgae EPRI EPRI Rio Tinto Rio Tinto TERI (India) TERI (India) PNNL PNNL Arizona Public Services Arizona Public Services ENEL Produzione ENEL Produzione Ricerca Ricerca Gas Technology Institute Gas Technology Institute 17 St. Helena, CA Wastewater Treatment Ponds St. Helena, CA Wastewater Treatment Ponds 18 19 20 . Antenna Size and Photosynthetic Efficiency Photosynthetic Electron-Transport Chain 200 Chl 20 20 20 20 20 20 20 20 20 20 Photosynthetic Electron-Transport Chains 21 SOLAR EFFICIENCY TRAIN FOR PHOTOSYNTHESIS SOLAR EFFICIENCY TRAIN FOR PHOTOSYNTHESIS . Standard / Optimistic assumptions re. losses in photosynthesis Incident Solar Radiation Percent Percent Factors Limiting Photosynthesis Lost Remaining Restricted to Visible Radiation 55 45 Losses to reflection, inactive absorption 20 / 10 36/40 Efficiency of primary reactions of PS 75 / 70 9 / 12 Respiration and dark metabolism 33 / 15 6 / 10 Light saturation and photoinhibition 50 / 10* 3 / 9 * 10% Loss assumes overcoming these limitations (see next slides) 1% Efficiency is about 33 t/ha/yr dry weight biomass production. Maximum is about 100 (higher plants) to 300 (microalgae?) t/ha-yr 22 Solar energy is diffuse, its energy content is low!! At a very favorable location: 5 kWh/m 2 /day = 6.6 GJ/year Under optimistic assumptions: 10% conversion efficiency $15 per GJ --> $10 H 2 /m 2 /year A AA more realistic assumptions: 3 % conversion efficiency $5 per GJ (based on current $30/barrel crude oil) $1 H 2 /m 2 /year 23 INTRODUCTION TO PHOTOBIOLOGICAL H 2 PRODUCTION INTRODUCTION TO PHOTOBIOLOGICAL H 2 PRODUCTION Many different photobiological H 2 production processes both direct and indirect, single and two stage, microalgaeor photosynthetic bacteria, have been studied for 30+ years. No practical applications have resulted. Some processes even lack a laboratory demonstration of the proposed reaction. For one example: direct biophotolysis, which produces H 2 directly from H 2 O without intermediate CO 2 fixation. Direct biophotolysis is the Holy Grail of H 2 production, due to its perceived high efficiencies. Major projects ongoing at several National Labs, GCEP /Stanford U., UC Berkeley, TCAG/IBEA, others in U.S. and abroad. 24 March 2004, National Academy Sciences: The Hydrogen Economy: Opportunities, Costs Barriers and R&D Needs Advanced Direct Photobiological H2 Production March 2004, National Academy Sciences: The Hydrogen Economy: Opportunities, Costs Barriers and R&D Needs Advanced Direct Photobiological H2 Production H 2 production by direct cleavage of H 2 O mediated by photosynthetic microorganisms, without intermediate biomass formation, [direct biophotolysis] is an emerging technology at the early exploratory stagetheoretically more efficient than biomass gasification by 1 or 2 orders of magnitude. bioengineering efforts on the light harvesting complex and reaction center chemistry could improve efficiency several- fold... into the range of 20 -30 percent (solar to hydrogen) ...substantial fundamental research needs to be undertaken This presentation addresses the realism of these projections which are typical of claims and publicity for such processes. 25 SCHEMATIC OF DIRECT BIOPHOTOLYSIS 26 FROM Benemann et al (1973): H2 EVOLUTION BY A CHLOROPLAST-FERREDOXIN-HYDROGENASE REACTION (IN VITRO DIRECT BIOPHOTOLYSIS REACTION] FROM Benemann et al (1973): H2 EVOLUTION BY A CHLOROPLAST-FERREDOXIN-HYDROGENASE REACTION (IN VITRO DIRECT BIOPHOTOLYSIS REACTION] _____________________________________________________________________________ Assay Contents umoles H2/15 min ________________________________________________________ Basic System (spinach chloroplasts, ferredoxin, Hase) 0.25 " " + DCMU (inhibitor of O2 evolution) 0.00 " " - Light (dark) 0.00 " " + glucose + glucose Oxidase (O2 absorber) 1.21 " " + glucose + glucose oxidase + DCMU 0.00 Heated Chloroplasts 0.01 _______________________________________________________________ CONCLUSIONS: Reaction is very short lived (<20 min) and VERY sensitive to even the small amounts of O2 produced in the process (with O2 absorber reaction runs >hours) 27 PROBLEM #1 OF DIRECT BIOPHOTOLYSIS: O 2 produced by PS inhibits H 2 production PROBLEM #1 OF DIRECT BIOPHOTOLYSIS: O 2 produced by PS inhibits H 2 production The data fromBenemannet al., 1973, shows that the O 2 produced by photosynthesis strongly inhibits H 2 production, at well below 0.1% O 2 (< 30 ppb O 2 ) This is at least 1,000-fold below what is required! Inhibition is not due to O 2 inactivation of hydrogenase (Hase). Inhibition is due to the reaction of O 2 with the electron transfer system (e.g. ferredoxinor inHase). Development by biotechnology of an O 2 stableHasereaction is NOT plausible (on thermodynamic and other grounds). O 2 absorbers (e.g. glucose-glucoseoxidase) not practical photosynthesis needed to produce the O 2 absorbers. 28 DIRECT BIOPHOTOLYSIS: MECHANISM AND ISSUES Simultaneous, single-cell, single stage, H 2 and O 2 Production DIRECT BIOPHOTOLYSIS: MECHANISM AND ISSUES Simultaneous, single-cell, single stage, H 2 and O 2 Production O 2 H 2 O PSII PSI Ferredoxin Hydrogenase H 2 The fundamental problems of direct biophotolysis are: 1. The strong inhibitionby O 2 (from water) of H 2 evolution. 2. The high cost of photobioreactors(to capture light and H 2 ). 3. The production of highly explosiveH 2 :O 2 mixtures. 4. The low practical efficiencyof all photosynthetic processes. There are no plausible solutions to problems 1 to 3 (discussed next, Problem 4 was discussed above) 29 30 PROBLEM #2 OF DIRECT BIOPHOTOLYSIS: High Cost of Photobioreactors. PROBLEM #2 OF DIRECT BIOPHOTOLYSIS: High Cost of Photobioreactors. Any process that uses light for H 2 production must be contained inside a transparent photobioreactors For direct biophotolysisthephotobioreactor must cover the entire area of the process. Photobioreactorsare inherently expensive, due to major limitations in scale-up and unit sizes (< 100 m 2 ). Photobioreactor costs will be well above $100/ m 2 (even without cost of the tubes or other glazing materials). Photobioreactorsare unaffordable even at the highest possible solar conversion efficiencies (10% solar to H 2 ). 31 EARLY EXAMPLE OF PHOTOBIOREACTOR FOR H 2 PRODUCTION BY MICROALGAE (U.S., 1978) 32 Tubular Photobioreactors in Hawaii designed for H2 Production (20 m long tube manifold, inclined at 5%) 33 34 ALTERNATIVE PHOTOBIOLOGICAL H2 PRODUCTION PROCESSES: INDIRECT BIOPHOTOLYSIS ALTERNATIVE PHOTOBIOLOGICAL H2 PRODUCTION PROCESSES: INDIRECT BIOPHOTOLYSIS The limitations of direct biophotolysisfor H 2 production led to proposals for indirect biophotolysis in which: 1. CO 2 is first fixed into storage carbohydrates by microalgae(e.g. starch in green algae, glycogen in cyanobacteria) growing in low-cost open ponds. 2. The accumulatedpolyglucose(starch, glycogen) is then converted to H 2 in a second anaerobic stage in the light in photobioreactorsor in the dark in fermentation tanks. Separating the O 2 and H 2 producing reactions avoids O 2 inhibition, greatly reduces the size of thephotobioreactors (if any) and avoids production of explosive O 2 -H 2 mixtures. 35 First Indirect Biophotolysis Process used First Indirect Biophotolysis Process used . 10 N2-FIXING CYANOBACTERIUM (NOSTOC) N2-FIXING CYANOBACTERIUM (NOSTOC) 36 Proposed Indirect Biophotolysis Process: Could use Spirulina, a mass cultured microalga Proposed Indirect Biophotolysis Process: Could use Spirulina, a mass cultured microalga 37 Proposed Indirect Biophotolysis Process (2 nd Stage shown as a dark fermentation) 38 C 6 H 12 O 6 + 6 H 2 O 10 NADH + 2 FADH 2 + 6 CO 2 Photosynthesis (10% Solar Efficiency) 10 H 2 Dark Fermentation (80-85% yield from Glu) H 2 O + CO 2 h For high yields will need genetically engineered algal cell with high photosynthetic efficiency in producing carbohydrates and also high yields of H 2 production in the dark by fermentations. THESE ARE THE R&D CHALLENGES OF PHOTOBIOH 2 Indirect Biophotolysis with Dark Fermentation as 2 nd Stage with high H 2 yield - Schematic