Bio-Fuel and CO2 Capture by Algae Ami Ben-Amotz June 24, 2008

11th ICAP

Galway Ireland

Microalgal Bio-Fuel

Oil Price and Wars Feasible algae for Energy at above $??/barrel

1975

History Case Study the Alga Dunaliella for glycerin as oil

Dunaliella, Chlorophyta

, Volvocales

Marine unicellular alga Butcher, 1959

4atural Bloom of Dunaliella Halotolerant Eukaryotic Alga

Surviving in saturated salt (>32%)

To the Dead Sea

From Sea Water

Dunaliella, “Salt Loving Alga”

Dunaliella cell Eye spot (?) Golgi

Nucleus

Osmotic Glycerol

Nucleolus Mitochondria

Vacuole Starch Pyrenoid

β-Carotene globules

Cytoplasm elastic membrane, no cell-wall

Chloroplast

Photosynthesis in Dunaliella Sugar and Glycerol Biosynthesis

ISOOSMOTIC GLYCEROL Up to 60% in Dunaliella

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 only at above $60/barrel 1975

Algae & Oil Price 1975

oil price dropped down Dunaliella Project was stopped

Until then Search for High Value Algal Products Study!

Dunaliella Scale-Up

Biotechnology “Intensive Cultivation”

Dunaliella Biotechnology Intensive Plant, 4BT Ltd., Eilat, Israel, 100,000 m2

∫hν x dt

Dunaliella Biotechnology

Processing

DU ALIELLA Harvesting Westphalia Ltd., continuous centrifuges

Algal Paste

Dunaliella Spray Dried High β-Carotene Algal Powder

β-Carotene Dunaliella Powder Vacuum Packing

Dunaliella Capsules 300 mg dry powder/cap 20 mg β-carotene 9-cis/all-trans 1:1

Japan & Far East Market Price ~$4,000/kg algal AFDA (β β-Carotene Health Food) Total sale ~$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

Annual Microalgae Production Costs 4BT Dunaliella Plant versus Alternative Bio-Fuel Algal Plant (10 Hectares Plant Open Ponds) Dunaliella 4BT Ltd., Eilat, 2008

Alternative Algal Plant 2008(?)

Cost in US$/year 500,000 (20 workers)

?

Electricity ($0.125/KW)

180,000

?

Fertilizers (4,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

?

1,166,000

?

70 tons (2g/m2/day)

?

$17.00/kg

$0.34/kg ???

$4,000/kg algal AFDA

Algae cost for bio-fuel should be below $0.5/kg algal AFDW

Manpower

Total Yearly production of dry algae biomass

Cost of 1Kg dry microalgae Market Price

(β-Carotene Health Food) (β

Total sale ~$100 million/year

4BT Ltd., 4ikken Sohonsha Co., Dunaliella Breakdown of Production Cost

Major Production Costs 4BT Ltd., Eilat, Israel

Manpower Production Cost

Manpower (20), US$500,000/y Electricity ($0.125/KW) Fertilizers (4,P,K, Fe) and other chemicals

Domestic Land City Taxes, US$50,000/y 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 4BT 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 (4,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 4BT Ltd. Eilat, Israel

Seawater, $0.25/m3 Additional Costs: Filtration & Chlorination Production Cost Manpower Electricity ($0.125/KW) Fertilizers (4,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 4BT Ltd. Eilat Super Centrifuge ~ $750,000 (Westfalia, Germany)

High Electric Running Cost (24 hrs/day) Production Cost Manpower

Electricity ($0.125/KW), US$ 200,000/y Fertilizers (4,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

Production Cost Manpower

Electricity ($0.125/KW) Fertilizers (4, P, K, Fe) and other chemicals US$ 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

4BT Ltd. Eilat Fertilizers KNO3, NH4NO3 KH2PO4, H3PO4 (~$1.0/kg)

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 4Ox, plus minerals, plus?

Flue Gas

Algae ?

CO2

CO 2

The “Algal Bible”: “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)

Israel Electric Corporation Four Power Plants all coal One is FGD Plant (Ashkelon)

IEC Power Plant Ashkelon, Israel Only one FGD chimney (out of 8 in Israel)

IEC CO2- Generation Basic Scheme “Please make holes in the smokestack for algae”

S e a Smoke fan

ash collector

Flue gas

FGD

Microalgae pond

s h o r e

Israel Electric Corporation 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. I. Coal C,% = H,% =

LHV = 65.26 4.53

S,% = O,% =

0.63 8.49

II. Theoretical Flue Gas Composition.

V0= V0H2O= V0SO2= Vgasalfa=

III. Real Gas Composition Unit Load Excess Air Calculated Before FGD 3

Gas Volume, Nm /kg fuel

8.743

6.74 0.748

Unit Nominal Load 550MW 6170 kcal/kg H2O,% = 10.99 Ash,%= 8.85 N,% = Excess Air= V0CO2= V0N2= 0

1.25 100.00% 1.22

@6%O2

Alfa =

1.4

181MW 1.7 Calculated Before FGD

After FGD

12.10

13.52

5.33

4.41EV dry= 6.55 03 8.743 Vgas6%O2= 10.04 (Gas temperature 140 -50 C, density 1.3 kg/m3). 550MW 341MW 1.21 1.44 Measured Calculated After Before FGD After FGD FGD 10.04 10.318 11.59

CO2,% O2,%

13.93 16.19

12.13 14.10

13.30 4.7-5.12

11.802 6.04

10.51 5.37

10.07 8.19

9.01 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

190-200

292

249

223

~250

243 No data

208 No data

186 No data

~0

~0

~0

NOx,ppmv

297.00 3

~5

3

CO,mg/Nm CHcondensable

287 No data

Sulfur Particles,mg/Nm3

~0 46

SO3,mg/Nm

300

260

Flue Gas Processing Inside the FGD Chimney

Analysis of the FGD Flue Gas Mist Many Minerals at Low pH (variety of coals) ?

Mist (H2O) Flue Gas 13% CO2 4Ox Minerals Low pH

Seambiotic Algae Pilot Plant Within the IEC Power Plant area, Ashkelon, Israel

Ponds on Construction

Ponds on Construction

Under liner Geo-textile

PVC Liner

FGD Gas From the Chimney to the Algae Ponds

IEC Power Plant Free Seawater Supply ~ 450,000 m3/hr (Filtered & Chlorinated) The Pumps Production Cost Manpower Electricity ($0.125/KW) Fertilizers (4,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 ?

Sea water

IEC Power Plant Flue gas Free 4OX 4 fertilizer(?) Production Cost Manpower Electricity ($0.125/KW) Fertilizers (4,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 ?

?

annochloropsis Eustigmatophyceae Bio-Fuel or High W3 FA, EPA

Stock Algae Cultures in house

Stock Algae Cultures outside

Scale-Up Cultivation of

annochloropsis 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 (4,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 ?

annochloropsis 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

g biomass/L

1 0.8 0.6 0.4 0.2 0 Pure CO2

Flue gas of burner

Flue gas of IEC Power Station

Flue gas of burner

annochloropsis pond of 400m2 Open Raceways: simple, low cost and long lifetime

4atural Selection of Microalgae season and by the coal Spring-Summer Diatoms (brown/black) by

Diatoms Self Selected algae by the specified coal FGD flue gas (spring-summer algae)

Coal FGD Algae Selection 2005-2008 Dunaliella, Chlorophyceae Tetraselmis, Chlorophyceae

annochloropsis, Eustigmatophyceae

annochloris, Chlorophyceae Chlorococcum, Chlorophyceae Skeletonema, Bacillariophyceae

avicula, Bacillariophyceae,

SEAMBIOTIC/IEC FLUE GAS (FGD) ALGAL GROWTH DATA 2005-2008 Algae Shape & size (µm)

Sensitivity to contamination (H,M,L)

18-35

Sphere 10

L

X

7.0-8.0

~1

~20

All year

10-32

Oval 5x10

M

X

7.0-9.0

~1

~20

SpringAutumn

20-30

Sphere 1

M

X Z

5.5-7.5

~1

~20

AutumnSpring

10-25

Sphere 1.5

M

X Z

5.5-7.5

~1

~20

SpringSummer

20-35

Rods and clumps

M

X

7.0-8.0

~1

~20

Spring- Autumn

15-35

Oval 7x10

L

X

7.0-8.0

~1

~20

Marine Algal Species (Class)

Growth Season Israel

Chlorococcum (Chlorophyceae)

SpringAutumn

Dunaliella (Chlorophyceae)

annochloris (Chlorophyceae)

annochloropsis (Eustigmatophyceae)

avicula, Skeletonema (Bacillariophyceae)

Tetraselmis (Chlorophyceae)

(Months)

Growth Temp. Range (min-max ºC)

Contamination Treatment

pH Growth (range)

Maximal Biomass Density In pond of 15 cm depth (g/L)

Average Algal Productivity (g/m2/day) By Period

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 Solar light Scattering and reflecting properties of surface Absorption spectrum (depth of culture) Photosynthetic efficiency (25%) Light saturation (7-95%) Respiration, photo-respiration, excretion Photo-inhibition Temperature ================================== Mean daily solar intensity Energy productivity at 3% efficiency Algal biomass productivity (5 kcal/g)

Reduction (%) ------100 10% 90 50% 45 75% 11.3 60% 4.5 5% 4.3 10% 3.8 20% 3.1 =========================== Productivity 4,000 kcal/ m2/day 120 kcal/ m2/day 25 g/m2/day

Dunaliella Productivity 4BT, 2 g/m2/day

Flue gas Algae Productivity, 20 g/m2/day (Terrestrial plants productivity is up to 5 g/m2/day)

Harvesting Centrifuge or?

Alternative low cost harvesting Bio-Flocculation, Auto-Flocculation Filtration Production Cost Manpower

Electricity saving Fertilizers (4,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 ?

Harvesting by Filtration

Co-Bio-Flocculation

annochloropsis & diatoms

Annual Microalgae Production Costs 4BT Dunaliella Plant versus Seambiotic/IEC FGD Plant (10 Hectares Plant) Dunaliella 4BT Ltd., Eilat

Seambiotic/IEC Plant (estimated) Cost in US$/year

500,000 (20 workers)

120,000 (8 workers)

Electricity ($0.125/KW) & residual energy

180,000

30,000

Fertilizers (4,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

1,166,000

236,000

70 tons (2g/m2/day)

700 tons (20g/m2/day)

Cost per 1Kg dry microalgae

$17.00

$0.34

Market Price

$4,000

For Bio-Fuel cost should be below $0.5/kg algal dw

Manpower

Total Yearly production of dry algae biomass

β -Carotene Health Food

Flue Gas Microalgae Gross Chemistry Controlled by: 4utrients, Temperature, Light, Salinity, pH & the Applied Phycologists

Protein (food & feed) 20-50%

Cellular Lipids (bio-diesel?) TG, DG, MG, Polar & 4eutral

8-60%

Cellular Carbohydrates (bio-ethanol?) 20-60% Most other classes: Chrysolaminarin (β (1→3) glucose units Chlorophyceae: Starch (α α (1→4) glucose units

From the Algae to Bio-Fuel

Seambiotic made algae available in large quantity

Seambiotic Algae frozen algae stock, ~tons

Extraction and Processing of lipids and carbohydrates into bio-diesel & bio-ethanol

ALGAL BIO-FUELS Algal paste (~1 ton) was shipped frozen from Seambiotic Ltd., IEC, Israel to

Inventure, USA

Israel

USA

annochloropsis Bio-Diesel Seambiotic & Inventure

Algal Bio-Diesel

Seambiotic & Inventure Bio-Diesel Certificate of Analysis

annochloropsis Bio-Diesel

Seambiotic & Inventure Algal Bio-Ethanol Chrysolaminarin to Bio-Ethanol

Seambiotic Ltd.

Seambiotic Algae supports money raising (by others) Algae

Sent to

Amount (Kg)

Raising ($ million)

annochloropsis

GreenFuel Technologies Boston

200

10

Diatoms

GreenFuel Technologies Boston

300

12

Sapphire San Diego

22

50

Many others

500

???

annochloropsis

Mix

The Vision Utilization of electric power plant resources for growing selected marine microalgae at energy cost for valuable products and bio-fuels while considering the issue of CO2 sink to reduce global warming • Low cost flue gas, CO2 • Low cost seawater • Residual energy • Arid land • Low cost algal agriculture • All year algae production

SEAMBIOTIC Ltd. & ISRAEL ELECTRIC CO

•