Technologies for biodiesel and bioethanol. Emile van Zyl Johann Görgens

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Technologies for biodiesel and bioethanol production Emile van Zyl Johann Görgens Microbiology and Process Engineering Stellenbosch University jou kennisvernoot your knowledge partner Content 1. Why consider biofuels? 2. Biodiesel and bio-ethanol as renewable fuels 3. Biodiesel production 4. Bio-ethanol production from starch 5. Next generation technologies for bioethanol from starch 6. Future technologies for bio-ethanol from lignocellulose 7. Biorefinery concept 8. Discussion points

1 Why consider biofuels? Fossil fuel CO 2 Air pollution Fossil fuel Excess CO 2 in atmosphere Fuel Petrol

Greenhouse effect In past 150 years CO 2 levels raised from 280 ppm to >360 ppm, 30 ppm in the last 17 years! Alternative fuel Renewable resource CO 2 Closed carbon cycle! Sugar, starch, lignocellulose Vegetable oils Fuel Biodiesel and bio-ethanol

2 Biodiesel and bio-ethanol as renewable fuels Biofuels as renewable energy 1. Biodiesel and bio-ethanol recently gained much attention with the soaring crude oil prices 2. Biofuels has to date hardly made a dent in the use of petroleum fuels. Approx 2% of USA transport fuels, similar in EU 3. This is bound to change in the future with limiting oil resources, the treat of greenhouse gas production as well as global security risks associated with limiting oil resources = government interventions 4. EU and USA have +2025 targets of 25% biofuels RSA 2013: 8% ethanol, 2% biodiesel, 4.5% total (ASGISA and BEE government program)

Biofuels energy balance Ratio between energy produced as biofuel compared to fossil energy inputs Biodiesel: 3.2:1 Bio-ethanol from starch: 1.34:1 Bio-ethanol from sugarcane: 8:1 Bio-ethanol from lignocellulose 4-20:1 3 Biodiesel production

Feedstocks for biodiesel Conventional: Sunflower seeds Soyabeans Cottonseed Waste vegetable oil Unconventional: Jatropha Indigenous plants Micro algae Animal oil Process for Biodiesel Production SEED SODIUM HYDROXIDE METHOXIDE EXTRACTOR FILTER PRESS DRYER REACTOR OIL CAKE METHANOL GLYCEROL

4 Bio-ethanol production from starch Starch composition Wheat Triticale Rye Endosperm Bran Wheat germ

Starch composition -1,4-linkages -1,6-linkages Structure of amylopectin in raw starch Starch degradation Amylopectin = -amylase [ph 6.0; 95-105ºC; 90 min] Liquefaction step Small starch oligosaccharides

Starch degradation Small starch oligosaccharides G G G G G P P G G G G G = glucoamylase P = Pullulanase P G G G P G G G G [ph 4.5; 60-62ºC; 12-96 h] Saccharification step Glucose Sugar fermentation Glucose Yeast Ethanol C 6 H 12 O 6 Glucose [180] 2x C 2 H 6 O + 2x CO 2 Ethanol [2x 46] [2x 44] Ethanol Yield = 92/180 x 1.1 = 0.56

Ethanol production from starch Thermostable -amylase Glucoamylase Yeast Alcohol recovery Maize Wheat Triticale Rye Water Liquefaction Jet Cooker >100ºC >5-8 min Saccharification Fermentation Distillation & dehydration Storage tank Grinding Slurry tank Adjust ph to 6.0 Adjust ph to 4.5 Secondary Liquefaction 95ºC, ~90 min DDGS Fuel blending 5 Next generation technologies bio-ethanol from starch

Genencor introduce Stargen TM 1. Enzyme cocktail that eliminates reduced heating requirements and ph adjustments during the process 2. Enzymatic hydrolysis and fermentation performed in the same process vessel: Integration results in enzyme, time and cost savings Enzymatic hydrolysis of raw starch Treated with Aspergillus -amylase [Buleon, A., P. Colonna, V. Planchot, and S. Ball. 1998. Starch granules: structure and biosynthesis. Int. J. Biol. Macromol. 23:85-112.]

Ethanol production from starch Alcohol recovery Saccharification & Fermentation Distillation & dehydration Maize Wheat Triticale Rye Water Storage tank Slurry tank Grinding StargenTM Enzyme & Yeast Adjust ph to 4.5 DDGS Fuel blending Raw-starch degrading yeast? amylopectin -amylase& glucoamylase Yeast

Raw-starch degrading yeast? Glucose Yeast Ethanol Is this possible? Maize starch with recombinant amylolytic yeast growing. Stained afterwards with iodine to show starch degradation.

Ethanol production from starch Alcohol recovery Saccharification & Fermentation Distillation & dehydration Maize Wheat Triticale Rye Water Storage tank Slurry tank Grinding Amylolytic Yeast! Adjust ph to 5.0 DDGS Fuel blending 6 Future technologies for bio-ethanol from lignocellulose

Lignocellulose sources maize stover bagasse woodchips Miscanthus as energy crop Renewable biomass available 1. Residues Agriculture Maize residues 6.7 Mt/a (118 PJ/a) Sugarcane bagasse 3.3 Mt/a (58 PJ/a) Wheat straw 1.6 Mt/a (28 PJ/a) Sunflower residues 0.6 Mt/a (11 PJ/a) Agricultural subtotal 12.3 Mt/a (214 PJ/a) Forrestry industry Plantatation residues 4.0 Mt/a (69 PJ/a) Sawmill residues 0.9 Mt/a (16 PJ/a) Paper & board mill slurry 0.1 Mt/a (2 PJ/a) Forrestry industrie subtotal 5.0 Mt/a (87 PJ/a) 2. Energy crops From 10% of available land Total, annual basis 67 Mt/a (1 170 PJ/a) 84 Mt/a (1 470 PJ/a) 3. Intruder plants 8.7 Mt (151 PJ)

Lignocellulose composition Non-fermentable sugars high energy aromatics Sugarcane bagasse Hexoses (fermentable) Cellulose 46% Lignin 28% Xylan 25% Arabinan 2% Pentoses (fermentable) Cellulose hydrolyses and fermentation cellulose Enzyme hydrolysis glucose yeast Fermentation ethanol

Cellulose hydrolyses and fermentation Glucose yeasts Fermentation ethanol Cellulose hydrolyses and fermentation Acid swollen amorphous cellulose recombinant yeasts

Yeast grow on amorphous cellulose with production of cellulases [EG1] [REF] [CEL5] [SFI] Biorefinery Concept Process a range of raw materials to a range of value-added added products Justification: Volatile Agro and Fuel markets Seasonality of production Changes in market conditions for raw materials/products Starch to ethanol, CO 2 and DDGS plant has limited economic lifespan Plan for future profitability, based on co- products Integration of production streams in plant is key Develop a biotechnology industry based on renewable resources, not just a bio-fuel plant

Discussion points 1. Fossil fuel won t last! Biofuels are here to stay get used to it! 2. SA has potential to play in the biofuels arena; should not be too hasty and learn from others mistakes 3. Which crops will be used for biofuel production in South Africa? 4. Which technologies should be used and developed for biofuel production? 5. How can one ensure that biofuel production in South Africa will remain profitable during economic cycles? 6. Will biofuel production in SA be sustainable?

Thank you!