Algae Biorefinery - Concepts

Dr. Ulrike Schmid-Staiger

National German Workshop on Biorefineries 15th September 2009, Worms

schmid-staiger@igb.fraunhofer.de

Microalgae - microscopic small plants

Ubiquitous seawater freshwater soil air

About 40.000 different algae in marine water sytems Algae are consumed by mankind for thousand of years 40-50 Gigatons of carbon are fixed by marine algae every year

schmid-staiger@igb.fraunhofer.de

Algae biomass a sustainable renewable resource for fine chemicals and energy
Advantages of using microalgae as renewable resource Growth rate is 5 to 10 times higher compared to plants Essential for growth are sunlight, CO2, and anorganic nutrients like nitrogen and phosphorous Carbon dioxide emitted from combustion processes can be used as a source of carbon for algal growth (1 kg of dry algal biomass requiring about 1.8 kg of CO2). Microalgae can be cultivated in seawater or brackish water on non-arable land, and do not compete for resources with conventional agriculture. Microalgae biomass can be harvested during all seasons. The biomass is homogenous and free of lignocellulose.

schmid-staiger@igb.fraunhofer.de

Main components of microalgae

Algae

Proteins

Carbohydrates storage products -(1-4)-glucans -(1-3)-glucans, fructans sugars, glycerol only very low cellulose content storage lipids mainly TAGs

Lipids membrane lipids different lipid classes up to 40% of total lipids are PUFA solubilised by solvent extraction of wet biomass, then transesterification

valuable Compounds pigments antioxidants fatty acids vitamins anti -fungal, -microbial -viral toxins sterols MAAs

high content up to 50% of dry weight in growing cultures all 20 amino acids

up to 50% of DW with solvents extractable from wet biomass recovery by pressing out the dry and ruptured biomass

schmid-staiger@igb.fraunhofer.de

Valuable compounds from microalgae

Pigments / Carotenoids -Carotene Astaxanthin Lutein Zeaxanthin Canthaxanthin Chlorophyll Phycocyanin Phycoerythrin Fucoxanthin Antioxidants Catalases Polyphenols Superoxid Dismutase Tocopherols Fatty acids (PUFAs) DHA (C22:6) EPA (C20:5) ARA (C20:4) GAL (C18:3)

Vitamins A, B1, B6, B12, C, E Biotine Riboflavin Nicotinic acid Pantothenate Folic acid

Other / Pharmaceuticals Antifungal Antimicrobial Antiviral Toxins Amino acids, Proteins Sterols MAAs as light protectant

schmid-staiger@igb.fraunhofer.de

Utilization of microalgae biomass

Feed

Production
in closed PBR

Aquaculture Poultry breeding

Proteins
Food Chemical Building Blocks Bioenergy Biofuels
Bifunctional building blocks acids alcohols

Harvest
and

Processing
dewatering drying

Carbohydrates

Lipids Algae biomass fractionation valuable Compounds

Feed Food Cosmetics

Diesel Kerosene Methane Syngas

Fatty acids/lipids Pigments Vitamins Antioxidants Nutraceuticals

schmid-staiger@igb.fraunhofer.de

Sustainable Algae-based Processes

Input
Solar Energy Operating Power Nutrients N , P, Mg, K CO2 Microalgae Cultivation

Production

DSP
Concentrating Drying Extraction Wet Biomass

Output
Carbohydrates Proteins Lipids, PUFAs Antioxidants Pigments Silicates Residual Biomass Micronutrients (Fe, Zn, Mg)

Lignocellulose free Algae Biomass

CHP-Plant

Biogas Technology

Methane electr. Energy thermal Energy

Recycling

schmid-staiger@igb.fraunhofer.de

Comparison between different cultivation systems

System Light efficiency Temperature control Gas transfer Oxygen accumulation Biomass concentration Sterility Cost to scale-up Volumetric productivity Energy demand per kg biomass produced Raceway ponds Fairly good None Poor low low low low low high Tubular reactors excellent excellent Low-high high high high high high high Flat panel airlift reactors excellent excellent Low-high low high high high high low

Net energy production is possible !

schmid-staiger@igb.fraunhofer.de

Characteristics of the Flat Panel Airlift Reactor

deep-drawn PVC half-shells including the static mixers
High productivity by a sophisticated system of static mixers resulting in efficient light distribution to all algal cells and low shear forces effecting to the algal cells Low production cost of the reactor by construction of plastics High scalability and modularity Low energy consumption for inter-mixing due to airliftdriven intermixing A pure photoautotrophic production process - Low requirements of energy as sunlight as main energy source can be used static mixer main targeted flow Provides the possibility to grow all kind of algae with high productivity at high biomass concentration

schmid-staiger@igb.fraunhofer.de

Scale-up Step to a Pilot Plant

21,6 MJ/kg TS 64 MJ/kg TS 24 MJ/kg TS

Link of several reactor modules (with a volume of 180 litre each) and joint operation outdoors Production of algal products in the range of several hundred kilograms. Net energy production is possible, due to reduction of energy demand with scale-up

schmid-staiger@igb.fraunhofer.de

Comparison of the energy input per kg DW of different production systems

160 140 120 100

Energieaufwand / Energy demand (MJ/ kg DW)

80 60 40 20 0
Raceway Rohrreaktor horizontal, gepumpt* Rohrreaktor helical, gepumpt* Rohrreaktor vertikal, gepumpt** Flat Panel Reaktor, Uni Almeria* FPA , Subitec derzeit FPA , Subitec, Ziel

11
schmid-staiger@igb.fraunhofer.de

Sustainable Algae-based Processes

Input
Solar Energy Operating Power Nutrients N , P, Mg, K CO2 Microalgae Cultivation

Production

DSP
Concentrating Drying Extraction Wet Biomass

Output
Carbohydrates Proteins Lipids, PUFAs Antioxidants Pigments Silicates Residual Biomass Micronutrients (Fe, Zn, Mg)

Lignocellulose free Algae Biomass

CHP-Plant

Biogas Technology

Methane electr. Energy thermal Energy

schmid-staiger@igb.fraunhofer.de

Growth and Biomass Productivity in FPA-Reactors exemplary of Phaeodactylum tricornutum

Phaeodactylum tric.: Growth in FPA-Reaktor
30 25
Light intensity (E m-2 s -1)

1,6
1200

Prod. (g DW l-1d-1)

1,2 0,8 0,4 0,0

DW (g/l)

20 15 10 5 0 10 15 20 25 time 30

800

400

10

15

20
-1

25

biomass concentration (g DW l )

High biomass productivity at even high biomass concentrations due to efficient intermixing Dependency of biomass productivity of relative light intensity per cell Optimum biomass yield at relatively low light availability (g DW produced per mole of photons E).

Prod. (g DW l-1d -1); Ylight (g DW/E)

1,6 1,2 0,8 0,4 0,0 0,0 0,1 0,2 0,3 0,4 0,5 rel. light availability (E g DW -1d-1)
Y light (g DW/E)

schmid-staiger@igb.fraunhofer.de

Production of storage products in microalgae

Carbohydrates as energy storage product

Growing algal cells

lipids
valuable compound

pigments

valuable compound proteins

pigments lipids

carbohydrates

N- and P-limitation
proteins carbohydrates

pigments

valuable compound proteins

lipids carbohydrate s

Lipids as energy storage product

schmid-staiger@igb.fraunhofer.de

Energetic use: Microalgal lipid production

60 lipids (% of dry w eight) 50 40 30 20 10

Nanno.o. Nanno.l Chl.v. Nanno.o2

Optimized production
Lipid increase per day (%) 5 4 3 2 1 0

0 0 2 4 time (d) 6 8 10

0,2

0,4 0,6 0,8 rel. light availability (E g DW-1 *d-1 )

1,2

Microalgal lipid production depends strongly on available light per cell

schmid-staiger@igb.fraunhofer.de

Fatty acid composition

Growth phase
Chlorella vulg. - Wachstumsphase

Lipid phase
Chlorella vulg. - Lipidphase

C14:0 C20:0 C16:0

C18:2n6c

C20:0

C14:0

C16:0 C16:1n7 C18:0

C16:1n7 C18:0 C18:2n6c C18:1n9c

C18:1n9c

Gesamtlipidgehalt 9 % der TS

lsure

Total lipid content 9 % of DW

Total lipid content 45% of DW Main fatty acid: C18:1 oleic acid

schmid-staiger@igb.fraunhofer.de

Downstream Processing
Algae production Cell harvest Drying Cell disruption Extraction / Purification Products

from dry biomass Process line 1 2 3 Filtration Precipitation Fast expansion Flotation from wet biomass Fluid extraction org. solventsl / H2O Superheated steam Ball mill Supercritical fluids scCO2 Separation Spray drying High pressure homogenizer Fluid extraction org. solventsl / H2O

hydrophilic Proteins Starch Glycerine Vitamins Micronutrients

lipophilic Oils Fatty acids (PUFA) Carotenoids Steroids Residual biomass

FhG1

schmid-staiger@igb.fraunhofer.de

Slide 17

FhG1

Th e challenge for algal biomass harvesting is to take the very low cell density and concentrate it to a point where lipid extraction is possible (as much as 1000X) using the lowest possible cost and process options. Th erefore, energy-intensive processes such as centrifugation may be feasible for high-value products but are far too costly in an integrated system producing lower-value products, such as algal oils for biofuels applications.
Fraunhofer Gesellschaft, 12-09-2009

Sustainable Algae-based Processes

Input
Solar Energy Operating Power Nutrients N , P, Mg, K CO2 Microalgae Cultivation

Production

DSP
Concentrating Drying Extraction Wet Biomass

Output
Carbohydrates Proteins Lipids, PUFAs Antioxidants Pigments Silicates Waste Biomass Micronutrients (Fe, Zn, Mg)

Lignocellulose free Algae Biomass

CHP-Plant

Biogas Technology

Methane electr. Energy thermal Energy

schmid-staiger@igb.fraunhofer.de

Downstream processes of microalgae: Eicosapentaenoic acid (EPA)

part of the membrane lipids of algal chloroplasts occurs as one of the fatty acids of the monogalactosyldiglycerides cell disruption preextraction of the monogalactosyldiglyceride necessary only fatty acid ethyl esters or free fatty acids can be extracted by use of scCO2 transesterification of the monogalactosyldiglyceride
EPA Fatty acid Lipase/

Glycerol

Fatty acid

monogalactosyldiglyceride

Fatty acid ethyl ester

schmid-staiger@igb.fraunhofer.de

Glycerol

Ethanol Alkali-catalyst

EPA

Downstream processes of microalgae: Eicosapentaenoic acid (EPA)

Expansion

EtOH

Lipase/ KOH
Vorlagebehlter

EPA

Extraction Centrifugation Trans(2. steps) (filtration) esterification/ 1h, RT Saponification

scCO2-Extraction

scCO2 Source

Algae cultivation

Preextraction with transesterification

Extraction with scCO2

schmid-staiger@igb.fraunhofer.de

Downstream processes of microalgae: Astaxanthin

Expansion

Vorlagebehlter

Drying

Grinding

Astaxanthin oil

scCO2-Extraction

scCO2 Source

Algae cultivation

Drying and grinding

Extraction with scCO2

schmid-staiger@igb.fraunhofer.de

Energy conversion processes from microalgae

schmid-staiger@igb.fraunhofer.de

Schematic process of biodiesel production

schmid-staiger@igb.fraunhofer.de

Sustainable Algae-based Processes

Input
Solar Energy Operating Power Nutrients N , P, Mg, K CO2 Microalgae Cultivation

Production

DSP
Concentrating Drying Extraction Wet Biomass

Output
Carbohydrates Proteins Lipids, PUFAs Antioxidants Pigments Silicates Residual Biomass Micronutrients (Fe, Zn, Mg)

Lignocellulose free Algae Biomass

CHP-Plant

Biogas Technology

Recycling

Methane electr. Energy thermal Energy

schmid-staiger@igb.fraunhofer.de

Outlook: Integrated process for mass and energy based utilization of microalgae
Energie

H2O
ADP+ Pi +NADP+

CO2

Algal biomass
CalvinZyklus
ATP+NADPH+H+

Products: pigments -3-fatty acids vitamins

Lichtreaktionen

O2

CH2O

residual biomass

organic wastes

1,85 kg CO2 are fixed per kg algal biomass produced

NH4, PO4

recycling

CO2
digestion / codigestion

8 MJ electricity

Biogas
CHPS

12 MJ heat per m biogas

schmid-staiger@igb.fraunhofer.de

Demands to Microalgal Biorefinery Processes

Energy efficient algae biomass production process
high rate of photosynthesis, photobioreactor, CO2-utilization, net energy balance Product recovery solvents (which and quantity) extraction from wet biomass, avoiding energy intensive drying steps Residual biomass utilization free of lignocellulose, conversion to biogas by anaerobic digestion, Recycling of nutrients CO2, nitrogen, phosphate Water use quantity and quality

schmid-staiger@igb.fraunhofer.de

Thank you for your attention

Ulrike Schmid-Staiger, Ph.D. Fraunhofer IGB Nobelstr. 12 70569 Stuttgart Tel. +49-(0)711-970 4111 Email: schmid-staiger@igb.fraunhofer.de

schmid-staiger@igb.fraunhofer.de

Downstream processes of microalgae: Eicosapentaenoic acid (EPA)

100 90 80 70 60 Yield [%] 50 40 30 20
27,4 5,3 77,6 12,7

3. extraction 2. extraction 1. extraction

0,0 9,6

preextraction with EtOH wet Biomass shows better results than dried biomass only 2 extraction steps are necessary

10 0 2% dried biomass 2% wet biomass

schmid-staiger@igb.fraunhofer.de