KAUST - Future Fuels Workshop...KAUST - Future Fuels Workshop ... • Proposals for practical algae...

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Algae Biofuels John R. Benemann MicroBio Engineering, Inc.,

San Luis Obispo, California, [email protected]

KAUST - Future Fuels Workshop March 7, 2016, KAUST, KSA

KAUST - Future Fuels Workshop March 7, 2016, KAUST, KSA

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Macroalgae (Seaweeds): Green, Red and Brown

1,000, 2000 and 6,000 species respectively


1,000, 2000 and 6,000 species respectively

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San Luis Obispo, Calif. home of MicroBio Egineering, Inc.)


– can be found on most beaches…


– can be found on most beaches…

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MICROALGAE

Nannochloropsis

Cryptocodinium

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11 Division, 29 classes vs. 2/12 vascular plants Each species (>100,000), each strain is different11 Division, 29 classes vs. 2/12 vascular plants

Each species (>100,000), each strain is different

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Salt Evaporation Ponds, San Francisco Bay(from my airplane window, June 2012)

Silicon Valley

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here growing in salt ponds - varying salinities and nutrients determine species dominance)

…key is the ecophysiology

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Micro- & Macro-algae: CO2 and BiofuelsMicro- & Macro-algae: CO2 and BiofuelsMicro- and macro-algae are non-vascular plants - carry out same process of photosynthesis as higher plants:

H2O + CO2 + Photons Biomass (CHxOy) + O2

(also need N, P, K, Fe, S, Ca, Mg, Mn, Ni, Zn, V, Mo, etc.)A major difference: micro- or macro-algae growing in water can‘t access sufficient CO2 from the atmosphere.Microalgae require concentrated CO2 sources (such as power plant flue gases, etc.), for high productivity. Can also obtain CO2 from wastewaters and other sources).

Macroalgae can obtain CO2 from seawater, if water exchange and mixing are high (boundary layer issue).

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The promises of micro- & macro-algae biofuels: The promises of micro- & macro-algae biofuels:

• High biomass productivities vs. conventional crops

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Typical example of projections: land area required to replace 50% of current USA petroleum-diesel usage using corn, soybean, & algae… (~ 80,000 L /HA- YR!)

algae soybean

corn

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The promises of micro- & macro-algae biofuels: The promises of micro- & macro-algae biofuels:

• High biomass productivities vs. conventional crops

• Microalgae use land, water resources unsuited for crops

• Macroalgae also do not compete with agricultural crops

• Many culture systems: ponds, closed reactors, floating

• High content/production fuels/feedstocks: H2, CH2O, oils

• Use power plants, stationary CO2 sources; reduce GHGs

• Project low production costs, favorable LCA/GHG

• Co-produce biofuels with feeds, high value bioproducts

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SXPAND

23/ 2/ 2012, Coral Gables, Florida, President Obama: "We're making new investments in the development of

gasoline, diesel and jet fuel that's actually made from ... Algae.

If we can make energy out of that, we’ll be alright.“We can replace up to 17% of the fuel we import for transportation

with this fuel which we can grow right here in the USA”

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The Current Reality of Algae Biofuels The Current Reality of Algae Biofuels • Microalgae produced mostly for high value human foods

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Main microalga grown commercially: Spirulina: Almost all in paddle wheel mixed raceway ponds <1 ha

Main microalga grown commercially: Spirulina: Almost all in paddle wheel mixed raceway ponds <1 ha

Spirulina

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microalgae are produced now almost exclusively for nutritional products

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The Current Reality of Algae Biofuels The Current Reality of Algae Biofuels • Microalgae produced mostly for high value human foods

• Macroalgae (seaweeds) for foods and polysaccharides;

• Biofuels NOT produced commercially from any algae

• Production: Micro- ~40,000 mt, macro- ~>1 million mt

• Production costs: micro- ~>$10K/mt, macro- ~>$1K/mt

• Other applications: microalgae in wastewater treatment; macroalgae: IMTA - integrated multi-trophic aquaculture

• R&D Biofuels: $ billions microalgae since 2007, most USA much less for macroalgae, most in Europe, Korea, Japan

• Prospects: micro- & macro-algae biofuels long-term R&DNearer-term, particularly for KSA, is for animal feeds

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OUTLINE OF TALKOUTLINE OF TALK#1. Microalgae H2 Production –

The Continuing Saga

#2. Algae Carbohydrate Production –The Fermentation Gambit

#3. Microalgae Oil Production –The Biofuels Moonshot

#4. The Economics of Algal Biofuels

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Benemann, UBC, Jan 7, 2011

H2 bubbles

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#1. Microalgae H2 Production: the continuing Saga #1. Microalgae H2 Production: the continuing Saga • First report of H2 production in 1880s by cyanobacteria • First lab studies of green algae H2 production in 1940s • Proposals for practical algae H2 production in 1950s. • 1973 Energy Crisis ignites interest in algal H2 production • Microalgae H20 splitting to O2 + H2 published 1973, 74 • R&D over following two decades in algal H2 production • One R&D focus was ‘direct biophotolysis’ – impossible?• 2000 Election: both US political parties support H2 R&D • Renewable & algal H2 were DOE R&D focus 2000-2004 • Late 2004 DOE awards $~10 million for algal H2 R&D• After G.W. Bush re-election, in early 2005 DOE rescinds awards and administration shift to lignocellulosic ethanol

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Jackson and Ellms (1886): H2 Evolution by Anabaena cylindrica - collected from a pond, placed into glass bottle

Jackson and Ellms (1886): H2 Evolution by Anabaena cylindrica - collected from a pond, placed into glass bottle

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The Chloroplast-Ferredoxin-Hydrogenase SystemThe Chloroplast-Ferredoxin-Hydrogenase System –(Benemann et al., 1973): Splitting water with photons

Direct biophotolysis2H2O 2H2 + O2

Chloroplasts Ferredoxin

Hydro-genase

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Benemann et al (1973) Proc. National Academy Sciences : Chloroplast - Ferredoxin - Hydrogenase Reaction

in vitro direct biophotolysis (biological water splitting)

Benemann et al (1973) Proc. National Academy Sciences : Chloroplast - Ferredoxin - Hydrogenase Reaction

in vitro direct biophotolysis (biological water splitting) Assay Contents micromoles H2 /15 min_______________________________________________________ Basic System (Chloroplast-Ferredoxin-Hydrogenase) 0.25

“ " + DCMU (Control - inhibits O2 production) 0.00

" " - Light ( Control, in dark) 0.00

" “ + Ascorbate + DCPIP + DCMU (bypass PSII, no O2) 1.54

" " + glucose + glucose oxidase (consume O2) 1.40

" " + glucose + glucose oxidase + DCMU (Control) 0.00

using heated Chloroplasts (Control) 0.01_______________________________________________________________CONCLUSION: Direct biophotolysis severely limited by O2 produced

The basic system contained 0.8 mg chlorophyll of fresh spinach chloroplast fragments, 18 nmol of ferredoxin and 470 ug of hydrognase (both from Clostridium klyveri), 15 umol HEPES buffer pH 7.6, 1.5 umol MgCl2, 2 umol NH4Cl

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N2-fixing Anabaena cylindrica with heterocyststhe first alga, cyanobacterium I studied, early

1970s, demonstrating heterocyst function

N2-fixing Anabaena cylindrica with heterocyststhe first alga, cyanobacterium I studied, early

1970s, demonstrating heterocyst function

Heterocyst(N2NH3protein)

Akinete (a spore)

vegetative cells (produce O2) vegetative cells

Heterocystsare site of nitrogenase enzyme where it is protected from O2

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Model of Heterocystous Cyanobacteria for H2 Production -- “Indirect Biophotolysis” Model of Heterocystous Cyanobacteria for H2 Production -- “Indirect Biophotolysis”

Nitrogenase produces H2 in absence of N2, thus we can make H2 with this alga, split water

Benemann and Weare. "Hydrogen Evolution by Nitrogen-Fixing Anabaena cylindrica.“ Science 184, 175 (1974).

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LESSON: Nutrient limitation can be used to make algae work as catalysts that convert sunlight into products without biomass production:

PHOTOSYNTHESIS FACTORIES

Expt. stopped

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1998

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“Microalgae biotech could be a huge source of H2 fuel”Jae Edmonds, World Industrial Biotech Congress, 2004“Microalgae biotech could be a huge source of H2 fuel”Jae Edmonds, World Industrial Biotech Congress, 2004

0

50

100

150

200

250

300

350

400

1990 2005 2020 2035 2050 2065 2080 2095

EJ/y

ear

BiomassElectrolysisCoalGasOilBiotechnology

Direct biological production of H2.

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#1. Microalgae H2 Production: the continuing Saga #1. Microalgae H2 Production: the continuing Saga • First report of H2 production in 1880s by cyanobacteria • First lab studies of green algae H2 production in 1940s • Proposals for practical algae H2 production in 1950s. • 1973 Energy Crisis ignites interest in algal H2 production • Microalgae H20 splitting to O2 + H2 published 1973, 74 • R&D over following two decades in algal H2 production • One R&D focus was ‘direct biophotolysis’ – impossible?• 2000 Election: both US political parties support H2 R&D • Renewable & algal H2 were DOE R&D focus 2000-2004 • Late 2004 DOE awards $~10 million for algal H2 R&D• After G.W. Bush re-election, in early 2005 DOE rescinds awards and administration shift to lignocellulosic ethanol

• Algal H2 production R&D continues, in many countries.

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CONCLUSIONS:Algae make H2! But >40 years ofapplied R&D, not yet demonstrated a single plausible mechanism to produce H2 fuel!

A CAUTIONARY TALENot all R&D leads to success

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The Continuing Saga




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Seaweed culture is a traditional technology Seaweed culture is a

traditional technology

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Seaweed Culture: Porphyra sp. (Nori)Seaweed Culture: Porphyra sp. (Nori)

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But on $ $ basis microalgae >20% of total

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Stinking mats of seaweed (Sargassum) piling up on Caribbean beaches

Stinking mats of seaweed (Sargassum) piling up on Caribbean beaches

Cancun, Mexico, Aug 8 2015

Puerto Rico , August 8 2015

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Peter Neushul, 1989 “Seaweeds for War: California’s WWI Kelp Industry “

Peter Neushul, 1989 “Seaweeds for War: California’s WWI Kelp Industry “

Over 1 million tons of Macrocystis pyrifera harvested and fermented by bacteria into ~10 million gallons of acetone (+ butanol, potash) in San Diego, California, 1916-1919, during WW1, for British Navy, needed for cordite manufacturing)

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Late 1970’s: Conceptual Design of a 400 hectare “Food and Energy - Open Ocean Seaweed Farm” Late 1970’s: Conceptual Design of a 400 hectare “Food and Energy - Open Ocean Seaweed Farm”

Methane production from kelp by anaerobic digestion

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Adult Macrocystis pyrifera Plant Adult Macrocystis pyrifera Plant

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http://www.scribd.com/doc/16595766/Seaweed-Feasibility-Final-Report#scribd

“Techno-Economic Feasibility Analysis of Offshore Seaweed Farming for Bioenergy and Biobased Products”Roesjadi, Coppinger, Huesemann, Forster, Benemann, March 2008, PNNL (Pacific Northwest National Laboratory)

California Kelp (Macrocystis pyrifera)

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History of US Department of Energy macroalgae projects –

major conclusions

History of US Department of Energy macroalgae projects –

major conclusions

John BenemannMicroBio Engineering, Inc., San Luis Obispo, California

February 11, 2016Washington DC.

US Dept. Energy ARPA-E Macroalgae Workshop

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Huesemann et al. 2012 Bioresource Technology “Acetone-butanol fermentation of Marine Microalgae” (US DOE Pacific Northwest National Laboratory)

Fermentation of kelp [Saccharina sp.] Butanol and total solvent yields were 0.12 g/g and 0.16 g/g, respectively. Improvements needed to make industrial seaweed fermentations economically feasible

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Recently proposals for seaweed biofuels in Europe , Korea, Japan, etc. - combine seaweed biofuels

with offshore wind, bivalve or fish aquaculture, etc.

Recently proposals for seaweed biofuels in Europe , Korea, Japan, etc. - combine seaweed biofuels

with offshore wind, bivalve or fish aquaculture, etc.

47Image: B. H. Buck (AWI)

The Challenge of Open Ocean Seaweed Cultivation

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The Continuing Saga




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Production of Microalgae for FuelsProduction of Microalgae for FuelsUS DOE Aquatic Species Program : Algae-to-Oil based on Benemann et al., 1978, 1982, UC Berkeley US DOE Aquatic Species Program : Algae-to-Oil based on Benemann et al., 1978, 1982, UC Berkeley

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J. Sheehan, P. Roessler, T. Dunahay, J. Weissman J. Benemann(Principal Investigator)

Paul Roessler prior Joe Weissmanat Synthetic Genomics now at ExxonMobilNow at Algenol in Florida

THE US DOE AQUATIC SPECIES PROGRAM - 1980 – 1996

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“The year was 1975, and my professor in Berkeley asked me if I wanted to change the world, and I said, sure, lets grow algae, that started it…”

ExxonMobil 30 sec TV spot, 2010-11

… From a 2010 TV Advert by ExxonMobil

… From a 2010 TV Advert by ExxonMobil

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Interview by Charlie Rose, PBS, with CEO Rex Tillerson, ExxonMobil, March 12, 2013.

Charlie Rose: “…in a 2009 joint venture with J. Craig Venter’s Synthetic Genomics, Exxon predicted it could produce fuels in 5 to 10 years”

Rex Tillerson: “Exxon is at Least 25 Years away from making fuel from algae ” … “We’ve come to understand some limits of that technology, or limits as we understand it today, which doesn’t mean it’s limited forever”

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Joule, Red Rock Biofuelsto merge, Nov 12, 2015

Layoff 60+ workers…CEO Serge Tchuruk (former CEO of Total) returns to board role

Algenol CEO Paul Woods resigns Oct 23, 2015

Lay off 45+ staffWoods stays on board Investments

total in both: ~$ ½ billion

Two examples of algae biofuel companies that promised much but failed to deliver… Two examples of algae biofuel companies that promised much but failed to deliver…

54… could we produce low cost algae oils?

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Can algae oil compete with other crops?

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40 ha biofuels demonstration plant,New Mexico40 ha biofuels demonstration plant,New Mexico

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Sept 8 2009: The Sapphire Energy launches their 150 mpg "Algaeus" on 10-day US tour

(but only used 1 gallon of algae oil for this!]

Sept 8 2009: The Sapphire Energy launches their 150 mpg "Algaeus" on 10-day US tour

(but only used 1 gallon of algae oil for this!]

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Professor Robert Dibble takes the Algeus for a spin…

Professor Robert Dibble takes the Algeus for a spin…

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However, the Algeus was not the first car running on algae oil: Ramin Yazdani (Davis, CA) made ~ 1 barrel of B10 algae biodiesel in his backyard refinery using an extract of

However, the Algeus was not the first car running on algae oil: Ramin Yazdani (Davis, CA) made ~ 1 barrel of B10 algae biodiesel in his backyard refinery using an extract ofextract of Dunaliella salina extract I gave him (December 2005). Ran his diesel Mercedes ~1,500 miles with it

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BASF Dunaliella salina production of beta-barotene in Australia (100 ha ponds)

(A plant now being constructed in KSA by a NAQUA and BASF joint venture]

BASF Dunaliella salina production of beta-barotene in Australia (100 ha ponds)

(A plant now being constructed in KSA by a NAQUA and BASF joint venture]

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NAQUA Dunaliella Ponds (South of Jeddah]

Jeddah 150 km

1 km2

shrimp ponds

NAQUA Dunaliella Ponds (South of Jeddah]

Jeddah 150 km

1 km2

shrimp ponds

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NAQUA (KSA) Shrimp Ponds Partial ViewDunaliella

ponds

NAQUA (KSA) Shrimp Ponds Partial ViewDunaliella

ponds

63Botryococcus braunii

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WAKE and HILLEN, Melbourne, AustraliaIn 1976 a "bloom" estimated at 1500 to 3000 ton… the alga has a high liquid hydrocarbon content, sufficient to cause flotation of the algal colonies. … hydrocracked to produce a distillate: 67% gasoline, 15% aviation fuel, 15% diesel fuel, 3% residual oil

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Petrobras, Universidade Federal do Rio Grande do Norte, launch algal biofuels pilot

Extremoz , April 3, 2012

Petrobras, Universidade Federal do Rio Grande do Norte, launch algal biofuels pilot

Extremoz , April 3, 2012 “The production of microalgae is a priority of the research projects of Petrobras, because of their yield potential, and is active in the absorption of CO2 and water cleaning. ”

Miguel Rossetto, President, Petrobras Biofuel

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The Continuing Saga




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The Continuing Saga



#4. The Dismal Economics of Algal Biofuels

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U.S. Department of Energy Office of Energy Efficiency & Renewable Energy

U.S. Department of Energy Office of Energy Efficiency & Renewable Energy

Ryan Davis et al. “Process Design and Economics for Production of Algal Biomass Open Pond Systems”

2,000 ha unlined ponds, 20% solids paste (afdw), 84 mt/ha-year with CO2 input cost at $45/mt, with systems designs provided by: Leidos Engineering – Crump (novel serpentine pond designs); Global Algae Innovations - Hazlebeck (0.1% sloped ponds)MicroBio Engineering - Woertz, Lundquist, Benemann (standard raceway ponds - Benemann et al, 1982; Lundquist et al., 2010) Harris Group, Lukas and Sexton (review of MicroBio Engineering)

CONCLUSIONS: Avg. biomass selling price: $500/mt for a 4 ha pond design by Microbio Eng. (lower than the others)

NREL/TP-5100-64772 February 2016 NREL/TP-5100-64772 February 2016

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Example of Schematic of Standard Raceway Ponds Example of Schematic of Standard Raceway Ponds

CO2 SumpPaddle Wheel

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Ponds, Christchurch 5 Ha 4 ponds, $<500K Dr. Rupert Craggs, NIWA, New Zealand (Ponds destroyed by earthquakes, rebuilt in N. island)

Sump for CO2 transfer Paddle wheel

Lamellar settler harvesting

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Earthrise Nutritionals, LLC, California, 2015 ~20 ha of Spirulina production ponds

Earthrise Nutritionals, LLC, California, 2015 ~20 ha of Spirulina production ponds

Linablue Plant(Open July 31, 2015)

Larger PondsPlant expansion area

Today >99% of all commercial autotrophic microalgal biomass produced in open ponds, >95% in paddle wheel mixed raceway ponds

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Global Algae Innovation (Hazlebeck) DesignGlobal Algae Innovation (Hazlebeck) Design

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Hawaii Bioenergy – Global Algae Innovations LLC US DOE Algae Biofuels Project in Hawaii

Hawaii Bioenergy – Global Algae Innovations LLC US DOE Algae Biofuels Project in Hawaii

Gravity fed series of ponds,up to about ~1.3 ha,

no paddle wheel mixing

Power Plant(for CO2)

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Leidos Co. Serpentine Design Leidos Co. Serpentine Design

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Site of MicroBio Engineering Inc. DOE NETL project to capture CO2 from a Florida coal-fired power plant to algae for fuels / feeds

78“We seem to have a few problems going from lab-scale to full-scale production”

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THE POTENTIAL AND PROMISE OF MICROALGAEcurrent feed crops vs. future algae feed/fuel crops

THE POTENTIAL AND PROMISE OF MICROALGAEcurrent feed crops vs. future algae feed/fuel cropsU.S. ANIMAL Avg. Yield Protein millions ha Total ProteinFEED CROP mt/ha-yr mt/ha-yr Harvested 1,000 mt/yr

CORN GRAIN 8.6* 0.86 28 24,100 SOYBEAN 2.7* 0.95 30 28,500MICROALGAE 100** 50 1 50,000

*Actual Yields dry matter and current acreage harvested ** Projected future yield for microalgae; typical protein content, 1 million ha harvested, produce 100 million mt biomassWould rival 10% global or all of US animal feed production … and may allow for net fossil CO2 emission reductions

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Benemann, April 12 2015, Ministry of Agriculture, KSA Roadmap for Algal Industry Development in the Kingdom

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COOIan Woertz

Neal Adler

CTO: Tryg Lundquist

Matt Hutton Ruth Spierling Braden Crowe

CEO: John Benemann

THANK YOU!

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Delhi, CA, Algae Wastewater Treatment Plant Two ~1.5 Ha raceway paddle wheel mixed pondsDelhi, CA, Algae Wastewater Treatment Plant

Two ~1.5 Ha raceway paddle wheel mixed ponds

Site of Cal Poly / Microbio Engineering US DOE-Funded Project

Paddle wheels

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