Promise of cassava in biorefinery

1. Cassava and Starch Technology Research Unit Promise of cassava in biorefinery Assoc. Prof. Dr. Klanarong Sriroth Cassava and Starch Technology Research Unit Kasetsart University and National Center for Genetic Engineering and Biotechnology

2. Cassava and Starch Technology Research Unit What is Biorefinery? A facility that integrates biomass conversion processes and equipment to produce multiple products including fuels, power and chemicals from biomass. (Source: National Renewable Energy Laboratory, NREL, http://www.nrel.gov) BIOMASS + REFINERY

3. Cassava and Starch Technology Research Unit Petroleum refinery Fossil Energy Polyethylene Ethylenoxide Ethylene Ethanol Propylenoxide Propylene Acrylnitrile Butadiene C4-mixture Polystyrene Benzol Nylon Toluol Polyurethane Polyester Xylol Alkyd resin Methanol Synthetic gas Ammonia Intermediate products Primary chemicals

4. Cassava and Starch Technology Research Unit Biorefinery Natural and Solar Energy Carbohydrates (Sugars, Starches, Cellulose) Alcohols Organic acids Lignins Nitrogenous compounds Proteins Sugar and derivatives Lipids / Fats Furan Etc. Other substances (Vitamins, Pigments, Flavors etc.) Primary chemicals Intermediate products

5. Cassava and Starch Technology Research Unit Biorefinery VS. Petroleum refinery Alcohols Organic acids Nitrogenous compounds Sugar and derivatives Phenol, Furan Fatty acid Syngas Etc.

6. Cassava and Starch Technology Research Unit Petroleum refinery • Raw materials • : cheap, homogenous, available • : limited, non-renewable • Processing / Conversion technology • : approved, highly optimized, continuous, bulk production • : physical & chemical process (distillation, cracking, • reforming, alkylation, polymerization & isomerization) • : less environmentally friendly • (sulphur dioxide, hydrocarbon vapors, smoke, smell) • Products • - flexible, multifunctional, accepted • - mostlynon-biodegradable, less environmentally friendly

7. Cassava and Starch Technology Research Unit Biorefinery • Raw materials • : cheap, heterogenous, abundant • : renewable • Processing / Conversion technology • : physical, chemical & biological process • : more environmentally friendly • Products • Multi-products (fuels, power, chemicals, materials) • Multi-functional (energy, health, pharmaceuticals, • Adhesives, detergents, antioxidants, packaging etc.) • biodegradable, environmentally friendly

8. (biodegradable) Cassava and Starch Technology Research Unit

9. Cassava and Starch Technology Research Unit Biorefinery Biomass Produces Conversion Processes Bio- Products • Fuels • Power (electricity, heat) • Chemicals • - Materials • Agricultural crops • Agricultural residues • Forest biomass • Grasses • Animal wastes • Municipal solid waste • Bioprocess • - Chemical process • Physical process • Combination • (Enzyme, Microbial fermentation, Thermo-chemical, Pyrolysis, Gastification, Steam explosion etc.)

10. Cassava and Starch Technology Research Unit Chemicals Materials Fuel/ Energy • Organic acids • Lactic acid, succinic acids • citric acid, acetic acid, • Nitrogenous compounds: • MSG, amino acids • Sugars & Derivatives • Xylitol, Sorbitol • Furfural, hydroxy furfural • Bioethanol: Yeast fermentation • Biodiesel: Transesterification • Biogas: Biomethylation • Biodegradable plastics • Polylactic acid (PLA), • Polyhydroxyalkanoates (PHAs) • Poly(butylene succinate) (PBS) • Fiber • 1,3 propanediol (PDO) • Resins • Foams • Nanofiber

11. Cassava and Starch Technology Research Unit Biomass 1. Agricultural crops 2. Agricultural residues 3. Wood chips and residues 4. Waste streams / by-products from household and industry

12. Sugar-based biorefinery industry Cassava and Starch Technology Research Unit First generation feedstock • Sugar crop: sugar cane, beets, sweet sorghum • Starch crop: corn, wheat, potato, rice, cassava Second generation feedstock Cellulose Lignocellulosic Hemicellulose Lignin

13. Potential feedstock in Thailand Potential feedstock in Thailand Cassava and Starch Technology Research Unit

14. Sugarcane Sugarcane Cassava and Starch Technology Research Unit

15. Cassava Cassava Cassava and Starch Technology Research Unit

16. Cassava and Starch Technology Research Unit Agricultural practices and agronomic traits of major sugar crops

17. Cassava and Starch Technology Research Unit Chemical composition of harvested agricultural produces from various starch crops 1 The numbers in parenthesis represent the percentage of composition on dry basis. In case of the reported values are in the range, the midpoints are used for dry basis calculation. Source: 2 Eckhoff and Watson (2009); 3 Treadway (1967); 4 Pomeranz (1998); 5 Juliano (1993); 6 Breuninger et al. (2009) Reported as: 7 Starch; 8 Starch and sugar

18. Cassava and Starch Technology Research Unit Cassava: Harvested area, production and yield of major countries 2004-2008 Source: Food and Agriculture Organization of the United Nations (FAO), 2009 The Top 10 Cassava Production Based on year 2008

19. Cassava production in Thailand Cassava and Starch Technology Research Unit Note : 1 hectare = 6.25 rai

20. Cassava and Starch Technology Research Unit Cassava plan (2008 – 2011) *1 ton cassava produces 167L of ethanol with 360 day/year production Source: Office of Agricultural Economics, 2008

21. 1st Generation 2nd Generation Sugar crops Starch crops Agricultural residues Lignocellulosic materials Starch Pretreatment Cooking / Enzyme hydrolysis Enzyme hydrolysis Sugar Sugar Sugar Fermentation Cassava and Starch Technology Research Unit

22. Cassava and Starch Technology Research Unit Production process of ethanol Mash Distillation Dehydration Enzyme hydrolysis Anhydrous ethanol Fermentator Production process of polylactic acid (PLA) Catalyst Gypsum Enzyme hydrolysis Purification Lactic acid Lactide PLA Fermentator Production process of polyhydroxyalkanoate (PHAs) Enzyme hydrolysis PHAs Extraction/ Purification Fermentator

23. Cassava and Starch Technology Research Unit Liquid fuels Beverage industry Chemical industry - green solvents Ethanol (CH3CH2OH) Cosmetic industry • Chemical feedstock • - ethyl lactate • acetic acid • ethyl acetate Pharmaceutical industry

24. Cassava and Starch Technology Research Unit Food industry - acidulants - preservatives - flavours - pH regulators - improving microbial quality Chemical industry - descaling agents - pH regulators - neutralizers - chiral intermediates - green solvents - cleaning agents Chemical feedstock - propylene oxide - acetaldehyde - propanoic acid - ethyl lactate - poly (lactic acid) - dilactide Cosmetic industry - moisturizers - skin-lightening agents - pH regulators - anti-acne agents - humectants - anti-tartar agents Biodegradable plastics Lactic acid (CH3CHOHCOOH) Pharmaceutical industry - dialysis solution - mineral preparations - tablettings - prostheses - surgical sutures

25. Cassava and Starch Technology Research Unit Bioplastics Bioplastics Biodegradable Biomass-based – Plastics which are broken down by microorganisms into carbon dioxide and waterand the biodegradability must behigher than 60% byinternational analysis method – Plastics which include more than 25% biomass origin raw materials – Biodegradability not concerned –Raw material origin notconcerned Source: Japan BioPlastics Association (JBPA)

26. Cassava and Starch Technology Research Unit Biodegradable* / Compostable** Earth Friendly PBAT PCL PBSA PBS Modified PET PLA PHA PHBV Starch-based polymer Petroleum-based Bio-based Conventional plastic Bio-PE PET ABS PS PVC Bio-PET Bio-PA PP LDPE HDPE Least Earth Friendly Non-Biodegradable / Non-Compostable *A plastic in which the degradation results from the action of naturally occuring microrganisms(bacteria, fungi and algae) to yield CO2, H2O. **A plastic that are biodegradable under controlled composting conditions (specified humidity,temperature, microorganisms and timeframe) to yield CO2, H2, inorganic compounds and biomass at a rate consistent with other compostable materials and leave no visible, distinguishable or toxic residue(within 180 days, ASTM 6900).

27. Cellulose Lignocellulosic Hemicellulose Lignin Cassava and Starch Technology Research Unit Use of starch in bioplastic Raw material Processing Applications First generation feedstock Fermentation Ppolymerization Sugar crop: sugar cane, beets, sweet sorghum Starch crop: corn, wheat, potato, rice, cassava Monomers (Lactic acid, succinic acid) Polymers Polylactic acid, PBAT Disposable, Semi-durable & Durable Second generation feedstock Plastic bag, Food container, Mulch film Processing additive Plasticizers, Lubricants Product additive Water, Heat, Light, Wear, Impact, Pesticide resistance, etc. Color, Titanium dioxide, Carbon black, fiber reinforcement; cellulose, etc. Filler Calcium carbonate Starch Cellulose Injection molding Compression molding Extrusion Film blowing Thermoforming Masterbatch

28. Cassava and Starch Technology Research Unit Promise of cassava in Thai bioplastics Starch • Use as monomer, i.e. glucose for microbial fermentation • Use as polymer

29. Cassava and Starch Technology Research Unit Promise of cassava use as sugar in bioplastics Cassava Starch Sugar Fermentation Ethanol PHB Lactic acid Bio-Polypropylene Bio-Polyethylene (Green Polyethylene 2011) PLA

30. Cassava and Starch Technology Research Unit Promise of cassava use as polymer in bioplastic Starch Enzyme hydrolysis As monomer (GLUCOSE) As polymer (STARCH) Microbial fermentation - Granular - TPS Starch / polymer blends • Starch materials • Foam • Film • Adhesive • Superabsorbent Monomer Polymer Polymerization • Other polymers • Natural: rubber, cellulose • Synthetic: PBAT, PBS Starch graft copolymers

31. Cassava and Starch Technology Research Unit Poly (lactic acid) - PLA Cassavaroot (7.2 Tons) Starch (1.8 tons) L-lactic acid (1.3 tons) PLA (1 ton)

32. Cassava and Starch Technology Research Unit Thai Root Production 29.6 million tons (1.7 baht/kg) 50,361 million baht Value 50,361 million baht Value Added 1.31 fold 40.4 % 57.1 % 2.5 % Dried Chip Local 1.11 million ton (4.0 baht/kg) Export 4.02 ล้านตัน (4.71baht/kg) 23,389 million baht Pellets Export 0.33 million ton (4.4 baht/kg) 1,458million baht Native Starch Local 1.29 ล้านตัน (9.0 baht/kg) Export 2.52 ล้านตัน (11.71 baht/kg) 41,105 million baht 65,964 million baht Ethanol 0.12 million liter (20 baht/liter) 2,429 million baht Animal Feed (Chip/Pallet) 24,373 million baht Local consumption cassava starch 1.29 million tons (9.0 baht/kg) 11,610 million baht Export cassava starch 2.52 million tons (11.71 baht/kg) 29,495 million baht Value Added 1.5 fold Native starch 0.6 million tons Native starch 0.5million tons Native starch 0.12million tons Modified starch 0.12 million tons (14.5 baht/kg) 1,740 million baht Sweeteners 0.5 million tons (16.0 baht/kg) 8,000 million baht Other products (Food industry, MSG, Paper) 9,715million baht 75,752 million baht Cassava chips 0.53million tons (Expected) Native starch 0.4 million tons (Expected) Value added 1.96fold Value added 1.8fold PLA 0.2 million tons (100 baht/kg) 20,000 million baht 98,532million baht 91,071 million baht

33. Thermoplastic starch (TPS) Granular starch Other polymers Granular starch Additives / plasticizers TPS and Melted Polymer Starch / polymer blend Starch / polymer blend Other polymers Cassava and Starch Technology Research Unit Use of starch in polymer blends Granular starch Thermoplastic Starch (TPS) • Particulate-filled composite • Blend properties affected by size, shape • and degree of adhesion with the matrix • Polymers (hydrophilic starch granules/ • hydrophobic polymer matrix) • - 40% or less of starch • Cooking starch above Tg and Tm with plasticizers • Destructurized starch as undergone melting and disordering of molecular and granular structure • Blend properties affected by starch structure and • their rheological propertiesas well as processing, • additives (modified from Gould et al., 1990)

34. Cassava and Starch Technology Research Unit Some characteristics of starch granules from different botanical sources Source: Swinkels (1998); Ozturk et al. (2009); Corn Refiners Association, Inc; Jane (2000); n.a. = not available

35. Cassava and Starch Technology Research Unit Some characteristics of corn and cassava starches 1121C, 15 min with 500s-1;2pH 3;31000 s-1;44C overnight; 3g dry starch in 25g water; 620% (w/w) Source: Mishra and Rai, 2006.

36. Cassava and Starch Technology Research Unit Modification of starches Improved functionality Technology tools • Size • Hydrophobicity • Electrical characteristic • Density • Crystallinity • Tg & Tm • Flow behavior index • Heat stability • Acid stability • Water holding capacity • Viscosity • Film forming properties • Mechanical properties • Opacity • Esterification • Etherification • Crosslinking • Grafting • Dextrinization • Thinning • Oxidation • Radiation • Hydro-thermal • Enzyme

37. Cassava and Starch Technology Research Unit

38. Cassava and Starch Technology Research Unit Cassava-based thermoplastic starch / Cassava-based materials

39. Cassava and Starch Technology Research Unit Corn-based Cassava-based

40. Cassava and Starch Technology Research Unit

41. Cassava and Starch Technology Research Unit Fiber diameter : 200 – 2,000 nanometer Starch in total solid : 5 – 40% by weight • Human hair ~ 10 micrometer • ~ 10,000 nanometer • 1/50 – 1/5 of human hair

42. Cassava and Starch Technology Research Unit Research and Development

43. Cassava and Starch Technology Research Unit Forms of starch: granular starch, modified starch, and TPS Composite materials : PLA, PVA, LDPE, PBAT, cellulose, and lignin Additives : Flame retartdant, nanoparticle, impact resistant 2010 1970’s Griffin et.al.introduced granular starch pellet as particulate filler in PE Otey et.al. developed gelatinized starch plastic system

44. Cassava and Starch Technology Research Unit • Fermentation : • Microorganism selection and modification for higher yield • & pure products • Use of lignocellulosic residues from cassava crops as feedstock • Fermentation technology for purer product • Cost-effective process of purification • Processing : • Novel starches with improved functionalities • (water resistant, heat resistant, high strength) • Optimization of processing conditions 2010

45. Cassava plants Stalk Cassava roots Leaves Ensiling/silage Peel / Stem In-field fertilizer Starch extraction Drying Pulp Starch Chips Animal feed Combustion electricity Biotechnological Conversion Chemical Conversion Extrusion Direct use Energy Gasification Co-extrusion Glucose Decomposition Ether formation Plasticization Fermentation Hydrogenation Red-Animation Esterification Bio-plastic Ethanol Co-and mix- polymers Lignin Hemicellulose Cellulose Glucosamine Methanol Starch esters Syngas PHB Sorbitol Starch ethers Cassava and Starch Technology Research Unit CASSAVA BIOREFINERY

46. Cassava and Starch Technology Research Unit Thank you for your attention