Bio-Fuel and CO2 Capture

by Micro-Algae
Ami Ben-Amotz
Wind, Sea and Algae
April 20-22, 2009
Maribo, Denmark
Microalgae
Algal Taxonomy, Storage Products
 Algal
Taxonomy
Pigments
Algal Pigments (HPLC)
Algae Taxonomy
Lipids
Assay by
GC
Nile Red (?)
 %

0
5
10
15
20
25
30
12:0

14:0

14:1

15:0

16:0

16:1

16:2

16:3

16:4

17:0

17:1

18:0

18:1

)6n-(18:2

)6n-(18:3

)3n-(18:3

)3n-(18:4

20:0

20:1

20:2

20:3

20:4
Algal Fatty Acids (GC)

20:5

20:6

22:0

)3n-(22:6
08S
TTR
NAN

24:0
NAN+NV

unknown
 Algal Taxonomy

Protein, Amino Acids

&
Molecular Biology
Commercial
Microalgae
Facilities
 Open Ponds
since 1950
Taiwan & Japan
round & oblong open ponds
mostly mixotrophic cultivation
Far East Chlorella and Spirulina
Earthrise Spirulina, Imperial Valley, CA, USA
Cyanotech Co, Spirulina
Hawaii, USA
Microbio Resources, Imperial Valley,
Dunaliella, Calipatria, CA, USA
Cognis Dunaliella, Whyalla, Australia
 Cognis, Whayalla, Australia
Large Scale Dunaliella Cultivation
Harvesting Facilities

Salt lagoon
Dunaliella, Hutt Lagoon,
West Australia
 Algatech Ltd., Israel
Large Scale Commercial Algal PBR
High value high price Haematococcus for astaxanthin
 Commercial Microalgae
High value high price health food products, cosmetics and mariculture
Microalgal Bio-Fuel
???
 Oil Price and Wars
Feasible algae for Energy at above $??/barrel
1975
 Past Case Study
the Alga
Dunaliella
for glycerin as oil
 Natural Bloom of Dunaliella
Halotolerant Eukaryotic Alga

Surviving in
saturated
salt (>32%)

To the Dead Sea

From Sea Water

 Dunaliella cell
Eye spot (?)

Nucleus Golgi

Nucleolus Osmotic
Glycerol
Mitochondria
Vacuole
Starch Cytoplasm elastic
membrane,
Pyrenoid no cell-wall

b-Carotene
globules Chloroplast
ISOOSMOTIC GLYCEROL
Up to 60% in Dunaliella
 Photosynthesis in Dunaliella
Sugar and Glycerol Biosynthesis
 The first Energy Crisis
1973-5
Algae for Energy
Large scale production of
Glycerol
by
Dunaliella
Energy Crisis 1975, Glycerol Algal Farm,
500 hectares in Sinai
 Oil Price and Wars
Feasible algae for Energy at above $100/barrel
1975
 Algae & Oil Price
1975
oil price dropped down
Dunaliella Project was stopped

Until then
Search for High Value Algal Products
Study!
 The Weizmann Institute Long Term
Dunaliella Research (nutrient optimization studies of 2x2 & 3x3)
The Weizmann Institute Long Term Dunaliella
Research (indoors, outdoor biotechnology)
The Weizmann Institute Long Term
Dunaliella Research (mutants & GMO)
 The Weizmann Institute Long Term
Dunaliella Research (outdoor biotechnology)
 The Weizmann Institute Long Term
Dunaliella Research (outdoor biotechnology)
 Scale-Up Key Issues
Seawater
Light
Carbonation & pH
Culture Mixing (waves)
Technology (engineering)
Predators Control
Applied Phycology Experience
Dunaliella
Scale-Up
Biotechnology
“Intensive Cultivation”
 Scale-Up
Area & Ponds Design
U or Ellipsoid Pond?
Pump, Bubbling air or Airlift?
Engineering Questions
 Dunaliella Biotechnology
Intensive Plant, NBT Ltd., Eilat, Israel, 100,000 m2 since 1990
 Dunaliella Scale Up

3,500m2

3,000m2

3m2
30m2

100m2

300m2
1,000m2
1,500m2
Mixing (waves)
Phycological Controlled Algae Farm
Dunaliella
Biotechnology
Processing
 DUNALIELLA
Harvesting Options
 DUNALIELLA Harvesting
Westphalia Ltd., continuous “clarifier centrifuges”

Algal Paste
Anhydro Spray Dryer
 Dunaliella
Spray Dried High b-Carotene Algal Powder
b-Carotene Dunaliella Powder
Vacuum Packing
Dunaliella Capsules
300 mg dry powder/cap
20 mg b-carotene
9-cis/all-trans 1:1
 Japan & Far East Market Price
~$4,000/kg algal AFDA
(b-Carotene Health Food)
Total sale ~$US 100 million/year

Final Product
Japan
Raw algae
Israel
 Dunaliella Health Food Powder
Door to door marketing by 500,000 sale agents in the Far East
Nature Beta Technologies Ltd. (NBT)
Nikken Sohonsha Co., Japan
sharing our know-how
 Major Production Costs
NBT Ltd., Eilat, Israel
CO2 Liquid Gas, $500/ton, 2008
Theoretical CO2 consumption: 2g/g algae
Actual CO2 consumption, 5-30 ton/month

Production Cost
Manpower
Electricity ($0.125/KW)

Fertilizers (N,P,K, Fe) and other chemicals

Domestic Land City Taxes

CO2 ($500/ton), US$150,000/y

Sea Water ($0.25/m3(

Fresh Water
Other supplies and Miscellaneous
Total
Yearly production of dry algae biomass

Cost of 1Kg dry microalgae

CO2 Input & Loss
Summer (>30°C) CO2 consumption: >10g/g
Actual summer consumption: 30 ton/month
 Major Production Costs
NBT Ltd. Eilat, Israel
Seawater, $0.25/m3
Additional Costs: Filtration & Chlorination

Production Cost
Manpower
Electricity ($0.125/KW)
Fertilizers (N,P,K, Fe) and other chemicals
Domestic Land City Taxes
CO2 ($500/ton)

Sea Water ($0.25/m3(, US$200,000/y

Fresh Water
Other supplies and Miscellaneous
Total
Yearly production of dry algae biomass

Cost of 1Kg dry microalgae

 Major Production Costs
NBT Ltd. Eilat
Super Centrifuge ~ $750,000
(Westphalia, Germany)
High Electric Running Cost (24 hrs/day)
Production Cost
Manpower

Electricity ($0.125/KW),
US$ 200,000/y
Fertilizers (N,P,K, Fe) and other chemicals

Domestic Land City Taxes

CO2 ($500/ton)

Sea Water ($0.25/m3(

Fresh Water

Other supplies and Miscellaneous

Total

Yearly production of dry algae biomass

Cost of 1Kg dry microalgae

 Major Production Costs
NBT Ltd. Eilat
Fertilizers
KNO3, NH4NO3
Production Cost
Manpower
KH2PO4, H3PO4
(~$1.0/kg)
Electricity ($0.125/KW)

Fertilizers (N, P, K, Fe) and other

chemicals US$ 36,000/y
Domestic Land City Taxes

CO2 ($500/ton)

Sea Water ($0.25/m3(

Fresh Water

Other supplies and Miscellaneous

Total

Yearly production of dry algae biomass

Cost of 1Kg dry microalgae

 Annual Microalgae Production Costs
NBT Dunaliella Plant
(10 Hectares Plant Open Ponds)
Dunaliella
NBT Ltd., Eilat, 2008
Cost in US$/year
Manpower 500,000
(20 workers)
Electricity ($0.125/KW) 180,000
Fertilizers (N,P,K, Fe) and other chemicals 36,000

Domestic Land City Taxes 50,000

CO2 ($500/ton) 150,000
Sea Water ($0.25/m3( 200,000
Fresh Water 20,000
Other supplies and Miscellaneous 30,000

Total 1,166,000
Yearly production of dry algae biomass 70 tons
(2g/m2/day)
Cost of 1Kg dry microalgae $17.00/kg
Market Price $4,000/kg algal AFDA
(b-Carotene Health Food)
Total sale ~$100 million/year
Dunaliella Book, May 2009
How to reduce
the
Cost of Algae
Production?
Electric Power Stations
Burn: oil, gas, coal and mix
Use: sea water for cooling
Average mid-large station emits ~ 4,000 ton CO2 per hr
CO2 emission, 4-14%, plus NOx, plus minerals, plus?
“Algal Culture, From Laboratory to Pilot Plant”
John S. Burlew (Ed.), 1953:
“Flue Gas is Toxic to Algae”! SO2 & H2S toxicity
 Flue Gas Desulphurization (FGD, SO2 Scrubbing)
FGD is the current state-of-the art technology used for removing sulfurdioxide
(SO2) from the exhaust flue gases in power plants that burn coal or oil to generate
the steam for the steam turbines that drive their electricity generatorsgenerators
 Flue Gas Desulphurization (FGD SO2 chemistry)
Scrubbing with a basic solid or solution
SO2 is an acid gas and thus the typical sorbent slurries or other materials used to remove
the SO2 from the flue gases are alkaline.
The reaction is taking place in wet scrubbing using limestone, CaCO3 to calcium
sulphite, CaSO3 that can be expressed as:
CaCO3 (solid) + SO2 (gas) → CaSO3 )solid) + CO2 (gas)

When wet scrubbing with a Ca(OH(2 )lime slurry), the reaction also produces CaSO3
(calcium sulphite) and can be expressed as:
Ca(OH)2 (solid) + SO2 (gas( → CaSO3 (solid) +H2O (liquid)

When wet scrubbing with a Mg(OH(2 )magnesium hydroxide slurry), the reaction
produces MgSO3 (magnesium sulphite) and can be expressed as:
MgOH2 (solid) + SO2 (gas) →MgSO3 (solid) + H2O (liquid)

Some FGD systems go a step further and oxidize CaSO3 (calcium sulphite) to produce
marketable CaSO4.2H2O (gypsum):
CaSO3 (solid) + 1/2 O2 (gas) + 2H2O (liquid) → CaSO4.2H2O (solid)
The Wet FGD Inside
 Israel Electric Corporation
Four Power Plants all coal
One is FGD Plant (Ashkelon)
 IEC Power Plant Ashkelon, Israel
One FGD chimney (out of 8 in Israel)
IEC, CO2 Generation Basic Scheme

S
e
a

s
Smoke fan ash h
Flue gas collector
o
FGD
r
e

Microalgae pond
 IEC Ashkelon Power Plant
The connections to the chimney
(FGD 2 units)
 FGD Power Station, Ashkelon, Israel (431 ton CO2 /hr, 10,344 /day)
Ruthenberg Power Station, Units III&IV. Unit Nominal Load 550MW
I. Coal LHV = 6170 kcal/kg
C,% = 65.26 H2O,% = 10.99
H,% = 4.53 Ash,%= 8.85
S,% = 0.63 N,% = 1.25
O,% = 8.49
II. Theoretical Flue Gas Excess 100.00%
Composition. Air=
0 0
V= 6.74 V CO2= 1.22 @6%O2 Alfa = 1.4
0 0
V H2O= 0.748 V N2= 5.33
0 0
V SO2= 4.41E- V dry= 6.55
03
alfa 6%O2
Vgas = 8.743 Vgas = 10.04
III. Real Gas Composition (Gas temperature 140 -50 C, density 1.3 kg/m3).
Unit Load 550MW 341MW 181MW
Excess Air 1.21 1.44 1.7
Calculated Measured Calculated Calculated
Before FGD After Before FGD After Before FGD After FGD
FGD FGD
3
Gas Volume, Nm /kg fuel 8.743 10.04 10.318 11.59 12.10 13.52

CO2,% 13.93 12.13 13.30 11.802 10.51 10.07 9.01

O2,% 16.19 14.10 4.7-5.12 6.04 5.37 8.19 6.10
N2,% 0.11 0.10 - 74.41 66.25 74.90 67.03
H2O,% 7.31 22.31 - 7.71 19.33 6.81 19.19
SO2,ppmv 504.23 - 56-70 427 - 364.37 -
H2S,% ~0 - ~0 ~0 ~0
NOx,ppmv 297.00 300 190-200 292 260 249 223
3
SO3,mg/Nm ~5
3
CO,mg/Nm 287 ~250 243 208 186
CHcondensable No data No data No data No data
Sulfur ~0 ~0 ~0 ~0
Particles,mg/Nm3 46
 Flue Gas Processing
Inside the FGD Chimney
 Seambiotic Algae Pilot Plant
IEC Coal Power Plant area, Ashkelon, Israel

Coal

Coal
Ponds on Construction
 PVC Liner
Long Duration (>15 years), Simple to Repair
 FGD Gas
From the Chimney to the Algae Ponds
 IEC Power Plant
Seawater Pumping ~ 450,000 m3/hr

Production Cost
Manpower

Electricity ($0.125/KW)

Fertilizers (N,P,K, Fe) and other

chemicals

Domestic Land City Taxes

CO2 ($500/ton)

Free Sea Water

Fresh Water

Other supplies and Miscellaneous

Total

Yearly production of dry algae biomass

Cost of 1Kg dry microalgae ?

Power Plant Seawater
Filtered & Chlorinated
 IEC Power Plant
Flue gas
Free NO X

N fertilizer(?)
Production Cost
Manpower
?
Electricity ($0.125/KW)

Fertilizers (N,P,K, Fe) and other

chemicals

Domestic Land City Taxes

CO2 ($500/ton)

Free Sea Water

Fresh Water

Other supplies and Miscellaneous

Total

Yearly production of dry algae biomass

Cost of 1Kg dry microalgae ?

 Nannochloropsis
Eustigmatophyceae
Bio-Fuel or High W3 FA, EPA
Stock Algae Cultures
in house
Stock Algae Cultures
outside
Scale-Up Cultivation of
Nannochloropsis sp
 Coal Burning FGD Flue Gas
Superior Algal Growth!
Algal density at depth of 20 cm ~ 1g algae/L

Production Cost
Manpower

Electricity ($0.125/KW)
Fertilizers (N,P,K, Fe) and other chemicals

Domestic Land City Taxes

*Free FGD CO2

Sea Water ($0.25/m3(

Fresh Water

Other supplies and Miscellaneous

Total

Yearly production of dry algae biomass

Cost of 1Kg dry microalgae ?

Algae Flue Gas
CO2
 Nannochloropsis Grows better on Coal FGD Flue Gas
than on Pure CO2
1. Pure CO2
2. Flue gas
3. Flue gas from the Power Plant
4. Flue gas

1.4

1.2

1
g biomass/L

0.8

0.6

0.4

0.2

0
Pure CO2 Flue gas of burner Flue gas of Flue gas of burner
IEC Power Station
 Coal FGD Mist Minerals Content
“Coal Extract” superior to “Soil Extract”

Minerals
?
13.3 % CO2
200 ppm NOx
Low pH
 Coal FGD Algae Selection
2005-2008
Dunaliella, Chlorophyceae
Tetraselmis, Chlorophyceae
Nannochloropsis, Eustigmatophyceae
Nannochloris, Chlorophyceae
Chlorococcum, Chlorophyceae
Skeletonema, Bacillariophyceae
Navicula, Bacillariophyceae,
 2009
Seambiotic Algal Pilot Plant, 1,000m2
Seambiotic 5 Hectares Algae Farm: End of 2009
Average Yearly Productivity
of
unicellular marine algae
on
FGD flue gas
in
open ponds
~20 g x m2 x day-1
Photosynthetic Limitation of Long Term Algal Productivity
Max Theoretical Algal Productivity
25 g/m2/day

Environment Factor Reduction (%)

Solar light ------- 100
Scattering and reflecting properties of surface 10% 90
Absorption spectrum (depth of culture) 50% 45
Photosynthetic efficiency (25%) 75% 11.3
Light saturation (7-95%) 60% 4.5
Respiration, photo-respiration, excretion 5% 4.3
Photo-inhibition 10% 3.8
Temperature 20% 3.1
================================== ===========================
Productivity
Mean daily solar intensity 4,000 kcal/ m2/day
Energy productivity at 3% efficiency 120 kcal/ m2/day
Algal biomass productivity (5 kcal/g) 25 g/m2/day

Dunaliella Productivity NBT, 2-4 g/m2/day

Flue gas Algae Productivity, 20 g/m2/day
(Terrestrial plants productivity is up to 5 g/m2/day)
 Algal
Feasible
Harvesting
Low Cost Algal Harvesting?

~ 15% solids

~ 0.1% solids
 Lower Cost Algae Centrifuges?
Basket Centrifuge

Decanter Centrifuge
Auto-flocculation
(Diatoms)
Harvesting by Floc-Filtration
Dunaliella induced Flocculation
 Co-Bio-Flocculation
Nannochloropsis & diatoms
 Microalgae Production Cost
NBT Dunaliella Plant versus Seambiotic/IEC FGD Plant
(10 Hectares Plant)
Dunaliella Seambiotic/IEC Plant
NBT Ltd., Eilat (estimated)
Cost in US$/year
Manpower 500,000 120,000
(20 workers) (8 workers)
Electricity ($0.125/KW) & residual energy 180,000 30,000

Fertilizers (N,P,K, Fe) and other chemicals 36,000 36,000

Domestic Land Taxes 50,000 10,000

CO2 150,000 5,000

Sea Water 200,000 5,000

Fresh Water 20,000 10,000

Other supplies and Miscellaneous 30,000 20,000

Total 1,166,000 236,000

Yearly production of dry algae biomass 70 tons 700 tons

(2g/m2/day) (20g/m2/day)

Cost per 1Kg dry microalgae $17.00 $0.34

Market Price $4,000 For Bio-Fuel cost should be
b-Carotene Health Food below
$0.5/kg algal dw
From the Algae
to
Bio-Fuel
Algae Paste of ~15%
 Dried Algae
Diatoms Nannochloropsis

‫אבקה‬
Seambiotic frozen algae stock
7 tons/1,000m2/year
 Extraction and Processing
of lipids and carbohydrates
to bio-diesel, bio-ethanol, protein
Algal paste (a few tons) were shipped frozen or dried
from
Seambiotic Ltd., Israel
to
processing trials

Israel
Seambiotic Algae: Analysis by NREL, the DOE, USA, Lipid Content (AFDW)
 Algal Fatty Acids
30

NAN
25
NAN+NV

TTR
20

08S
%

15

10

0
Nannochloropsis,Bio-Diesel
Seambiotic & Inventure
Seambiotic Algal Bio-Diesel (MeOH-HCl)
 Algal Bio-Oil Specifications
for
Low Cloud Point Jet-Fuel

No Cell Wall
High Content of TAG
Lower Chain Length Fatty Acids
Higher FA Saturation
Fatty Acids of Dunaliella bardawil (NBT)
Dunaliella bardawil**
NBT Ltd., Eilat, Israel
Dunaliella bardawil** (NBT)
 Stock of
4 tons
Spray Dried
Dunaliella bardawil**
is available in NBT
for
Jet-Fuel Processing
Seambiotic Algal Bio-Ethanol

Seambiotic Ltd.
 Flue Gas Microalgae Gross Chemistry
Protein (food & feed)
20-50%
Cellular Lipids (bio-diesel)
TG, DG, MG, Polar & Neutral, Long & Short FA
8-50%
Cellular Carbohydrates (bio-ethanol)
20-50%

Chlorophyceae: Starch (a (1→4) glucose units

Most other classes: Chrysolaminarin )β )1→3) glucose units
 Essential Amino Acids in Microalgae
(compared to soybean oil)
B
7

6
NAN

5 NAN+NV
A.A. (mg/100g)

TTR

4 08S

Soybean
3

0
 Microalgal Products
Commodity Market Potential Value
33% Protein (feed), US$ 1.0/kg = $ 0.3

33% Lipids (bio-diesel), 1.2 US$/L = $ 0.4

33% Carbohydrates (bio-ethanol), US$ 1.0/L = $0.3

Total ~ US$ 1.0/kg algae

Land or Ocean Algae Farming?
The Internet Vision
ISRAELI ELECTRIC CO