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GCEP Energy Workshop


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
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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)
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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.
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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
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Bessel Kok, 1973
Bessel Kok, 1973
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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)
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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
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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
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MICROALGAE R&D PONDS IN ROSSWEL, NEW MEXICO
MICROALGAE R&D PONDS IN ROSSWEL, NEW MEXICO
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Typical High Rate Pond Design
Typical High Rate Pond Design
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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)
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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
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St. Helena, CA Wastewater Treatment Ponds
St. Helena, CA Wastewater Treatment Ponds
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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
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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
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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
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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.
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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.
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SCHEMATIC OF DIRECT BIOPHOTOLYSIS
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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)
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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.
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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)
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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
).
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EARLY EXAMPLE OF PHOTOBIOREACTOR FOR H
2
PRODUCTION BY MICROALGAE (U.S., 1978)
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Tubular Photobioreactors in Hawaii
designed for H2 Production (20 m long
tube manifold, inclined at 5%)
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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.
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First Indirect Biophotolysis Process used
First Indirect Biophotolysis Process used
.
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N2-FIXING CYANOBACTERIUM (NOSTOC)
N2-FIXING CYANOBACTERIUM (NOSTOC)
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Proposed Indirect Biophotolysis Process: Could
use Spirulina, a mass cultured microalga
Proposed Indirect Biophotolysis Process: Could
use Spirulina, a mass cultured microalga
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Proposed Indirect Biophotolysis Process
(2
nd
Stage shown as a dark fermentation)
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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