Algae for HAlgae for H22 : The Perspective: The Perspective

Aparat MahakhantAparat Mahakhant

Microbiological Resources Centre (MIRCEN)Microbiological Resources Centre (MIRCEN)Thailand Institute of Scientific and Thailand Institute of Scientific and Technological Research (TISTR)Technological Research (TISTR)

EE--mail : mail : aparat@tistr.or.thaparat@tistr.or.th

ContentContent

Introduction to algaeIntroduction to algaeHydrogen production from algaeHydrogen production from algaeMarket for energy from algaeMarket for energy from algaeIntroduction to Algal Culture Introduction to Algal Culture Collection (ACC), Collection (ACC), MIRCEN, TISTRMIRCEN, TISTR

Introduction to AlgaeIntroduction to Algae

What are Algae ?What are Algae ?Large, heterogeneous, polyphyletic, Large, heterogeneous, polyphyletic, photoautotroph (Ophotoautotroph (O22 evolution )evolution )Lack differentiated root, stem, leaveLack differentiated root, stem, leaveChlorophyll Chlorophyll aa-- common 1common 1oo pigmentpigmentTerrestrialTerrestrial--aquatic (fresh/brackish/ marine)aquatic (fresh/brackish/ marine)Size 10Size 10--1212 m (m (picopico) to >10 m (seaweed)) to >10 m (seaweed)COCO22--fixation fixation (C(C--flux, Cflux, C--credit/GHG)credit/GHG)N & P uptake N & P uptake (eutrophication/3(eutrophication/3oo WWT)WWT)Storage: Storage: starchstarch, oil, , oil, high value substanceshigh value substances e.g. e.g. pigments, bioactive compoundspigments, bioactive compounds

Algae and Energy: Learning from HistoryAlgae and Energy: Learning from History

Over a century ago, pond Over a century ago, pond scum (scum (Anabaena Anabaena cylindricacylindrica, , a a cynobacteriumcynobacterium) collected ) collected from a Massachusetts from a Massachusetts reservoir was found to reservoir was found to produce almost pure Hproduce almost pure H22 gasgas(Jackson & (Jackson & EllmsEllms, 1896), 1896)Microalgae biofuel R&D Microalgae biofuel R&D mainly focused on Hmainly focused on H22production until 2006production until 2006

Algae and energy: Learning from HistoryAlgae and energy: Learning from HistoryAlso about a century ago, blooms of Also about a century ago, blooms of hydrocarbon producing green alga hydrocarbon producing green alga Botryococcus brauniiBotryococcus braunii washing washing onshore in Australia were collected onshore in Australia were collected & used as fuel& used as fuelMicroalgae biofuel were mentioned Microalgae biofuel were mentioned over 50 years ago, when algae pilot over 50 years ago, when algae pilot plant operated on a rooftop at MIT, plant operated on a rooftop at MIT, as part of R&D program that set the as part of R&D program that set the foundations for algae biomass foundations for algae biomass culture technology (Burlew, 1953)culture technology (Burlew, 1953)

BotryococcusBotryococcus bloombloom

Algae and Energy: Learning from HistoryAlgae and Energy: Learning from History

Algae biomass production for Algae biomass production for wwtwwt & & conversion to methane was studied at UC conversion to methane was studied at UC berkeleyberkeley since early 1950s (Oswald & since early 1950s (Oswald & GoluekeGolueke, 1960), 1960)The 1970s The 1970s ““Energy ShockEnergy Shock”” giving a boost giving a boost to R&D on algae for energy (to R&D on algae for energy (BenemannBenemann, , 1980)1980)The U.S. The U.S. DoEDoE Aquatic Species Program Aquatic Species Program (ASP, 1980(ASP, 1980--1996) managed by NREL, 1996) managed by NREL, studied microalgae oil production (Sheehan studied microalgae oil production (Sheehan et alet al., 1998)., 1998)

Algae and Energy: Learning from HistoryAlgae and Energy: Learning from History

From 1990From 1990--2000 a major program on 2000 a major program on microalgae for COmicroalgae for CO22 capture/utilization was capture/utilization was carried out in Japan, focusing on optical carried out in Japan, focusing on optical fiber closed fiber closed photobioreactorsphotobioreactorsIn 1990s a pilot plant using a combined In 1990s a pilot plant using a combined system of green algae and photosynthetic system of green algae and photosynthetic bacteria was operated within a power plant bacteria was operated within a power plant of Kansai Electric Power Co. Ltd. of Kansai Electric Power Co. Ltd. (Miyamoto, 1997)(Miyamoto, 1997)

MicroalgaeMicroalgae

Scenedesmus obliguusChlorella fusca

Platymonas subcordiformisGreen algae

Chlamydomonas reinhardtii

Oscillatoria limosaOscillatoria limnetica

Gloeocapsa alpicola Nostoc sp. Microcystis sp.

Anabaena cylindrica

Cyanobacteria (blueCyanobacteria (blue--green algae)green algae)

Hydrogen Production Hydrogen Production from Algaefrom Algae

Algae Production Systems ChallengeAlgae Production Systems Challenge

PresentPresentHigh value/Low volumeHigh value/Low volume

““SpirulinaSpirulina”” ““PhycocyaninPhycocyanin””““ββ--carotenecarotene””

FutureFutureHigh volume/Low value High volume/Low value

““BiofuelBiofuel”” (H(H22, bioethanol,, bioethanol,biodiesel)biodiesel)

Why Hydrogen?Why Hydrogen?

““Future energyFuture energy””RenewableRenewableNot evolve the greenhouse gas (CONot evolve the greenhouse gas (CO22) in ) in combustioncombustionLiberates large amount of energy per unit Liberates large amount of energy per unit weight in combustionweight in combustionEasier to converted to electricity by fuel cellsEasier to converted to electricity by fuel cells

Why Biological Hydrogen Why Biological Hydrogen Production?Production?

Biological hydrogen productionBiological hydrogen production by by photosynthetic microorganisms require photosynthetic microorganisms require simple solar reactor with low energy simple solar reactor with low energy requirement requirement Electrochemical hydrogen production via Electrochemical hydrogen production via solar batterysolar battery--based water splitting requires based water splitting requires solar batteries with high energy requirementsolar batteries with high energy requirement

General (Microalgal) Biomass Conversions ProcessesGeneral (Microalgal) Biomass Conversions Processes

MicroalgalBiomass

BiochemicalConversion

ThermochemicalConversion

ChemicalSeparation

DirectCombustion

Dark Fermentation

Anaerobic Digestion

Photo-Fermentation

Biophotolysis

Gasification

Pyrolysis

Liquefaction

Solvent Extraction

Power Generation

Hydrogen, Ethanol

Hydrogen, Methane

Hydrogen, Ethanol

Hydrogen

Hydrocarbon Gas

Oil, Gas, Charcoal

Oil

Oil

Electricity or Power

Source: U.S.A D.o.E. & Pacific Northwest National Lab.

Hydrogen Production ProcessesHydrogen Production Processes

ConceptsConcepts

ChallengesChallenges•• Low yields and solar conversion efficiencies for dark & photo Low yields and solar conversion efficiencies for dark & photo fermferm..•• Inhibition of Inhibition of hydrogenasehydrogenase by oxygen in direct biophotolysisby oxygen in direct biophotolysis•• Explosive gas mixtures in direct biophotolysisExplosive gas mixtures in direct biophotolysis•• Expensive Expensive photobioreactorsphotobioreactors and gas separationand gas separation

Culture Biomass Dark Fermentation Organic Acids + Solvents + H2

Organic Acids Photo-Fermentation by Photosynthetic Bacteria H2

Culture Biomass Direct or Indirect Biophotolysis H2 + O2

Source: U.S. D.O.E. & Pacific Northwest National Lab.

Life Cycle Energy AnalysisLife Cycle Energy Analysis

Energy Inputs Consist of:Energy Inputs Consist of:•• OperatingOperating energy needed for pumping COenergy needed for pumping CO22, mixing the pond, , mixing the pond,

pumping water, harvesting the biomass and converting it to Hpumping water, harvesting the biomass and converting it to H22•• EmbodiedEmbodied energy in fertilizers and other used chemicalsenergy in fertilizers and other used chemicals•• EmbodiedEmbodied energy (amortized) in capital equipmentenergy (amortized) in capital equipment(i.e., construction materials and energy used for construction)(i.e., construction materials and energy used for construction)

EOR ~ 10 for open pond cultures (EOR ~ 10 for open pond cultures (BenemannBenemann & Oswald, 1996)& Oswald, 1996)EOR ~ 10 for open pond cultures (EOR ~ 10 for open pond cultures (RudolfiRudolfi et al., 2007)et al., 2007)EOR EOR ≤≤ 1 for photo1 for photo--bioreactors (bioreactors (RudolfiRudolfi et al., 2007)et al., 2007)(EOR = Energy(EOR = Energy--output Ratio) output Ratio)

Objective: Fuel Energy Output > All Energy Inputs (EOR>1)

Problem of Direct Problem of Direct BiophotolysisBiophotolysis

Oxygen is a positive suppressor of hydAgene expression and inhibitor of the hydrogenaseH2 production by hydrogenase can only take place in anaerobic conditionThis incompatibility in the simultaneous O2 and H2 photoproduction has been a problem in 60-years of related research

Conversion of algal biomass to produce HConversion of algal biomass to produce H2, 2, Ike Ike et alet al., 1998 ., 1998

Fixation by microalgaeSolar energy

Carbon dioxide

Starch in algal biomass

Organic acids

Fermentation by anaerobic bacteria

Photoproduction by photosynthetic bacteria

Solar energy

Hydrogen

1st step

2nd step

3rd step

Indirect Indirect BiophotolysisBiophotolysis

Hydrogen Hydrogen productionproduction

Our StudyOur StudySelected starchSelected starch--producing BGA producing BGA strain: strain: Nostoc muscorumNostoc muscorum TISTR TISTR 88718871Anaerobic digestion of algal Anaerobic digestion of algal biomass: biomass: Lactobacillus brevissubsp. brevis TISTR 868Photosynthetic HPhotosynthetic H22 producing producing strain:strain:Rhodobacter sphearoidesRhodobacter sphearoides TISTR TISTR 15291529

Our ResultsOur ResultsWorking volume:Working volume: 600 ml600 ml

HH22 accumulation: 50accumulation: 50--60 ml 60 ml (almost pure)(almost pure)Starting time of production: Starting time of production: 1212--16 hours16 hoursDuration time of production: Duration time of production: 8 hours8 hoursHH22 production rate: 10production rate: 10--1212 ml/l ml/l culture/hculture/h

200～300 yen/㎥-H2

High cost for production of bio-hydrogenLimitation

Increase production efficiency: Continuous culture

To decrease the cost to less than 100 yen/㎥-H2

Decrease in cost for material supplement: Utilization of wastewater

Production of other useful compounds: Utilization of bacterial cells for functional foods & neutraceutical e.g. CoQ 10

Sources: Prof. Dr. Kazumasa Hirata, Osaka Univ., Pers. comm.

Opportunity from EOpportunity from E--W Perspective:W Perspective:Biofuel from Algae using NonBiofuel from Algae using Non--Freshwater SourcesFreshwater Sources

AlgaeAlgae--Based Production of Biofuels, Based Production of Biofuels, Co products, & Service w/ Impaired WatersCo products, & Service w/ Impaired WatersImpaired Water

- brackish groundwater- produced water- desalination concentrate- wastewater- Industrial wastewater- Municipal wastewater- Geothermal water & heat

Waste CO2 & Heat- Electric power generation- Industrial processing- Wastewater treatment- Desalination Co-Products

- feeds- fertilizers- biopolymers- glycerine- others

*PBRs = PhotoBioReactors

+ Hybrid Systems = Ponds + PBRs

Biomass Harvesting

Processing

Biofuels

- biodiesel - biogas

- ethanol - H2

Algae Production SystemsPonds, PBRs*, Hybrid Systems+

ReclaimedWater

- Nutrient removal

Sunlight(photoautotrophic)

Organic Carbon(heterotrophic)

O2

Biofixationof CO2

Source: Pate, Sandia National Labs. ABS, 2007

Co-product: CoQ 10Photosynthetic bacteria are useful materials forproduction of CoQ 10

well known as anti-ageing

The production of CoQ 10 and antioxidant activity were investigated in photosynthetic bacteria cultivated under basal conditions and H2-production conditions

Basal conditions

H2 productionconditions

Sources: Prof. Dr. Kazumasa Hirata, Osaka Univ., Pers. comm.

Lets see our previous results Lets see our previous results ((OscilltoriaOscilltoria okeniokeni TISTR 8549)TISTR 8549)

53.7853.7820.5920.59AshAsh2443.482443.484,028.934,028.93Total energy (cal./g)Total energy (cal./g)

21.5421.5424.0024.00CarbohydrateCarbohydrate0.840.840.190.19FiberFiber4.784.782.652.65FatFat

15.8515.8551.9451.94ProteinProtein3.213.210.630.63MoistureMoisture

Swine farm Swine farm effluenteffluent

BGBG--11 11 mediummedium

Composition (%)Composition (%)

Recent Status of HRecent Status of H22 from Algaefrom Algae

In Algae Biomass Summit In Algae Biomass Summit ““Algae for EnergyAlgae for Energy””Nov. 15Nov. 15--16, 2007, San Francisco, U.S.A. 16, 2007, San Francisco, U.S.A.

Dr. John R. Dr. John R. BenemannBenemann, Manager, , Manager, International International Network on Biofixation of CONetwork on Biofixation of CO22 and Greenhouse Gas and Greenhouse Gas AbatementAbatement mentioned in his presentation onmentioned in his presentation on

““A Brief History of Microalgae BiofuelsA Brief History of Microalgae Biofuels”” thatthat

““Microalgae biofuels R&D mainly focused on HMicroalgae biofuels R&D mainly focused on H2 2 production, until January 31production, until January 31stst, 2006, when H, 2006, when H22 fell fell

out of favorout of favor””

Market for Energy from Market for Energy from AlgaeAlgae

Market for energy from algaeMarket for energy from algae

In Algae Biomass Summit In Algae Biomass Summit ““Algae for EnergyAlgae for Energy””Nov. 15Nov. 15--16, 2007, San Francisco, U.S.A. 16, 2007, San Francisco, U.S.A.

Investor are becoming increasingly interested Investor are becoming increasingly interested in algae as the next big in algae as the next big ““playplay”” in the renewable in the renewable energy and clean technology space energy and clean technology space A session provided an opportunity for startA session provided an opportunity for start--up up companies to highlight their organization, companies to highlight their organization, projects & technologyprojects & technology

Market for energy from algaeMarket for energy from algaeMarket of interest included aviation fuel, Market of interest included aviation fuel, biogasoline, biodiesel, ethanol, methanol, biogasoline, biodiesel, ethanol, methanol, hydrogen and nutrition supplement for hydrogen and nutrition supplement for agricultural usesagricultural uses--nevertheless mainly nevertheless mainly focusedfocused on biodiesel for land on biodiesel for land transportation, commercial aircraft, military transportation, commercial aircraft, military jet fuel (JPjet fuel (JP--8) (Defense Advanced 8) (Defense Advanced Research Project Agency, DAPRA)Research Project Agency, DAPRA)

Market for energy from algaeMarket for energy from algae

BiodieselBiodiesel & bioethanol are more & bioethanol are more attractive than Hattractive than H22 because of their because of their downstream process are complete or downstream process are complete or nearly completenearly completeSteering committee formed for Algae Steering committee formed for Algae Trade AssociationTrade Association

Introduction to Algal Introduction to Algal Culture Collection Culture Collection

(ACC), (ACC), MIRCEN,TISTRMIRCEN,TISTR

Functions of ACC, TISTRFunctions of ACC, TISTR

ServicesServicesResearchResearch-- Research relevant to the Research relevant to the

collectioncollection-- Applied research on utilization Applied research on utilization

of microbial resourcesof microbial resources

Research conducted by Research conducted by ACCACC

Research relevant to the collectionResearch relevant to the collection-- Survey & collection of Survey & collection of algalalgal strains from strains from terrestrial & aquatic ecosystemsterrestrial & aquatic ecosystems

-- Taxonomy of algal strains using morphologyTaxonomy of algal strains using morphology-- LongLong--term preservation of algal strainsterm preservation of algal strains

cryopreservation encapsulation freeze-drying gelatin disc

Research conducted by Research conducted by ACCACC•Research and development of algal biotechnology for sustainable utilization of algal bioresources

-Agriculture

-Industry

-Environment

Utilized in paddy fields in all regions, especially in the central region of Thailand

Algal biotechnology for agriculture

Biofertilizer from N2-fixing BGA

“exclusive technology transfer”

“Alginure” Algotech Co., Ltd. > 10 years

“Organic Agriculture Certification”

Algal biotechnology for agriculture

Soil conditioner from polysaccharide producing BGA >150 strains in ACC

Insecticide

Cotton ball wormBeet army worm Hapalosiphon sp. TISTR 8252

Effect of crude extract of Hapalosiphon fontinalisTISTR 8225 on grass

Herbicide

Fungicide

Calothrix sp. TISTR 8906

Laboratory

arid

industry

mountainous

rubber tree

seaside

Algal biotechnology for paint industryAlgal biotechnology for paint industryResearch on the establishment of Thailand standard Research on the establishment of Thailand standard test test mmethod for determining the resistance of exterior ethod for determining the resistance of exterior emulsion paint to algaeemulsion paint to algae

standard strains On-site exposure

Paint IndustryPaint Industry

Thai Industrial Standard TIS Thai Industrial Standard TIS 23212321--2550 2550 ““Weather Resistant Emulsion PaintsWeather Resistant Emulsion Paints””Promulgated in Royal Gazette Promulgated in Royal Gazette InternationalInternational BiodeteriorationBiodeteriorationResearch Group (IBRG)Research Group (IBRG)--Annual meetingAnnual meeting--Round Robin TestRound Robin Test

Signing ceremony between TISTR and Siam Nostoc and Signing ceremony between TISTR and Siam Nostoc and Microalgae Co. Ltd.Microalgae Co. Ltd. on June 14on June 14thth , 2007, 2007““exclusively technology transfer on mass production of exclusively technology transfer on mass production of NostocNostoc ballball””

ACC at MIRCEN, TISTRACC at MIRCEN, TISTR

Race-way ponds 5,000-10,000 L

Thank you very muchThank you very much