Diluted acid pretreatment for an integrated microalgae bio-refinery to produce lipid- and carbohydrate-based biofuels

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1 Diluted acid pretreatment for an integrated microalgae bio-refinery to produce lipid- and carbohydrate-based biofuels Tao Dong, Lieve Laurens, Nick Nagle, Stefanie Van Wychen, Nicholas Sweeney, Philip Pienkos Algae Biomass Summit San Diego, California Sep. 30, 2014 NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

2 Introduction Integrated bio-refinery process for multiple products recovery from algal biomass Response of carbohydrate and lipids recovery under diluted acid pretreatment Biomass morphological changes in cellular structure after pretreatment Conclusion

3 Biomass fractionation for fuels & value-added chemicals Ethanol Fermentation Succinic acid Farnesene Proteins Lipids HDO/HI Blend stocks Aviation Fuel Green Diesel Animal feed Proteins AD fermentation, etc Isobutanol Bio-plastics Methane

4 Scheme for integrated algal biomass processing Algae Water Acid Steam Media KOH A-100 Feedstock A-200 Pretreatment Slurry A-300 S/L Separation Liquor A-500 Fermentation A-600 EtOH Recovery Fuel HL NC HL SD Hexane Solids NaOH Fatty acids (FAME) (% DW) Diesel equivalent (gallon/ton) Fermentable Sugars (% DW) Ethanol (gallon/ton) Total fuel energy (10 3 Btu/ton) Total GGE per ton biomass (GGE/ton) A-325 Extraction Liquor A-350 Lipid Recovery Solids Solids A-375 Protein Extract. Solids A-360 Anaerobic Digestion Liquor A-400 Butanol Ferm A-450 Butanol Recovery

5 Algal feedstock production at ASU Using a Combination of PBR s and Open Raceways Three Production Strains: Chlorella sp. Scenedesmus sp. Nannochloropsis sp. Three Growth Regimes: High Protein (Early) High Carbohydrate(Mid) High Lipid (Late)

6 Feedstock Composition and Rates of Lipid Accumulation Chlorella sp. Nannochloropsis sp. Scenedesmus sp. Early (high protein) Mid (high carbohydrate) Late (high lipid)

7 Acid Dilute-acid pretreatment to release lipid & carbohydrate CEM Explorer Microwave Reactor Automated system w/36-positions 300 watt output Stir bar mixing Rapid heating Central Composite Design 4.1% 145 ºC, 2% H 2 SO 4 0% 117 Track both fatty acid and carbohydrate release Temperature 175

8 Response of lipids recovery from different strains 80% 80% NC FFA TAG HL NC Element HL CZ HC CZ HL SD HC SD HL NC 90% 90% CZ Carbon Hydrogen FFA Nitrogen TAG Oxygen HC CZ HL CZ Sulfur Phosphorus <0.001 <0.001 < % 100% SD FFA TAG Mid HC Late HL HC SD HL SD

9 Response of carbohydrate recovery from different strains NC CZ SD Galactose/ Glucose Microalgae Rhamnose Mannose % (based on total carb) HCNC HLNC HCCZ HLCZ HCSD HLSD NC: Laminarin CZ: Starch SD: Glucomannan Mid HC Late HL

10 Energy yield from integrated algal biomass processing NC CZ SD SD CZ NC mid late late late Gasoline equivalent (gal/ton)** Btu equivalent (x10e3) Diesel equivalent (gal/ton) Btu equivalent (x10e3) Total fuel energy (x10e3 Btu/ton) Total GGE (GGE/ ton) Mid HC Late HL

11 Biomass morphological changes in cellular structure HL NC HL CZ HC SD

12 Conclusion Integrated microalgae biomass processing is able to recovery lipids and fermentable sugar. Acid concentration and temperature have combined effects for lipids and sugar recovery. The response of microalgae biomass to pretreatment is strain-dependent Achieve >100 GGE/ton for the late harvest Scenedesmus sp. and Nannochloropsis sp. strains.

13 Acknowledgements NREL Deborah Hyman Kelsey Ramirez Robert Sebag Paris Spinelli Chandler Ridler Earl Christensen ASU: John McGowen (ASU) Thomas Dempster (ASU) BETO

14 THANKS! QUESTIONS?

15 % DW FAME Lipids ash Carbohydrates Glucose Xylose Galactose Arabinose Mannose Protein HP NC HC NC HL NC HP SD HC SD HL SD HP CZ HC CZ HL CZ

16 Integrated processing of microalgae biomass

17 Hydrodeoxygenation (HDO) of Algae Oil Left: high-lipid Chlorella oil at 25 wt% in hexane Before After Right: Chlorella oil HDO product over Pd/C 450 C, 1300 psi H 2 Residence time ~2 min; LHSV = 1 hr -1 GC-MS: primarily C 15 and C 17 n-alkanes

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