Post on 13-Jan-2016
description
Promise of cassava in biorefinery
Assoc. Prof. Dr. Klanarong SrirothAssoc. Prof. Dr. Klanarong SrirothCassava and Starch Technology Research UnitCassava and Starch Technology Research Unit
Kasetsart University and Kasetsart University and National Center for Genetic Engineering and BiotechnologyNational Center for Genetic Engineering and Biotechnology
Cassava and Starch Technology Research Unit
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)
What is Biorefinery?
BIOMASS + REFINERY
Cassava and Starch Technology Research Unit
Petroleum refinery
Ethylene
Polyethylene
Ethylenoxide
Ethanol
PropylenePropylenoxide
Acrylnitrile
BenzolPolystyrene
Nylon
C4-mixture Butadiene
XylolPolyester
Alkyd resin
Toluol Polyurethane
Synthetic gasMethanol
Ammonia
Primary chemicals Intermediate products
Cassava and Starch Technology Research Unit
Biorefinery
Alcohols
Organic acids
Nitrogenous compounds
Sugar and derivatives
Furan
Etc.
Carbohydrates(Sugars, Starches, Cellulose)
Lignins
Proteins
Lipids / Fats
Other substances (Vitamins, Pigments, Flavors etc.)
Primary chemicals Intermediate products
Cassava and Starch Technology Research Unit
Biorefinery VS. Petroleum
refinery Alcohols
Organic acids
Nitrogenous compounds
Sugar and derivatives
Phenol, Furan
Fatty acid
Syngas
Etc.
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
- mostly non-biodegradable, less environmentally friendly
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
Cassava and Starch Technology Research Unit
(biodegradable)
Cassava and Starch Technology Research Unit
Biomass
Produces
Biorefinery
Conversion
ProcessesBio-
Products
- 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.)
- Fuels
- Power (electricity, heat)
- Chemicals
- Materials
Cassava and Starch Technology Research Unit
Fuel/ Energy- Bioethanol: Yeast fermentation
- Biodiesel: Transesterification
- Biogas: Biomethylation
Materials
- Biodegradable plastics
Polylactic acid (PLA),
Polyhydroxyalkanoates (PHAs)
Poly(butylene succinate) (PBS)
- Fiber
1,3 propanediol (PDO)
- Resins
- Foams
- Nanofiber
Chemicals- Organic acids
Lactic acid, succinic acids
citric acid, acetic acid,
- Nitrogenous compounds: MSG, amino acids
- Sugars & Derivatives Xylitol, Sorbitol
- Furfural, hydroxy furfural
Cassava and Starch Technology Research Unit
Biomass1. Agricultural crops
2. Agricultural residues
3. Wood chips and residues
4. Waste streams / by-products from household and industry
Cassava and Starch Technology Research Unit
First generation feedstock
Lignocellulosic
Second generation feedstock
Cellulose
Hemicellulose
Lignin
- Sugar crop: sugar cane, beets, sweet sorghum
- Starch crop: corn, wheat, potato, rice,
cassava
Sugar-based biorefinery industry
Cassava and Starch Technology Research Unit
Potential feedstock in ThailandPotential feedstock in Thailand
Cassava and Starch Technology Research Unit
SugarcaneSugarcane
Cassava and Starch Technology Research Unit
CassavaCassava
Cassava and Starch Technology Research Unit
Parameter Sugarcane Cassava
1. Crop duration 9-14 months 10-12 months
2. Growing season Only one season Beginning / after rainy period
3. Propagation method Cutting / Ratoon Cutting
3. No. of cycle in a year One One
4. Soil requirement Grow well in loamy soil Grow well in sandy loams and/or loamy sands
5. Water management/Requirement (m/ha)
Requires water throughout the year / 36,000
Less water requirement; less than 1,000 mm/year
6. Fertilizer input Greater fertilizer requirement Little fertilizer requirement
7. Crop management Require good management Less pest and disease; easy management
8. Harvesting Labor intensiveDecember – March
Manual and labor intensiveAll year round
9. Feedstock yield (tons/ha) 70 25
10. Sugar/ starch content (% by weight, wet basis)
8-15 30
11. Sugar/starch yield (tons/ha) 5.6-10.5 7.5
12. Other biomass Leaves Leaves, Stem
Agricultural practices and agronomic traits of major sugar crops
Cassava and Starch Technology Research Unit
Starch Crops Chemical composition (%wet basis)1
Moisture Protein Lipid Crude fiber Ash Carbohydrate
Corn grains2 7-23 6.2-13 (11.3) 2.4-5.3 (4.5) 6.4-11.1 (10.3) 0.9-3.6 (2.7) 49-737 (72.1)
Potato tubers3 78 2.2 (9.9) 0.1 (0.4) 0.4 (1.8) 1 (4.5) 17.18 (76.8)
Wheat grains4 15 13.6 (16.0) 1.7 (2.0) 9.4 (11.0) 1.5 (1.8) 58 (68.0)
Rice grain , paddy5 14 5-6.6(6.6) 1.3-2 (1.9) 14.1 (16.1) 2.5-4.5 (4.0) 55-63 (67.3)
Cassava roots6 59-70 0.7-1.2 (2.7) 0.1-0.4 (0.7) 0.6-1.1 (2.4) 0.5-1 (2.1) 26-38 (89.5)
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
Chemical composition of harvested agricultural produces from various starch crops
Cassava and Starch Technology Research Unit
Cassava: Harvested area, production and yield of major countries 2004-2008
Country Rank*
Harvested area (million ha) Production (million tons) Yield (tons/Ha)2004 2005 2006 2007 2008 2004 2005 2006 2007 2008 2004 2005 2006 2007 2008
World 18.00 18.47 18.34 18.55 18.70 203.11 207.09 222.29 224.13 232.95 11.29 11.21 12.12 12.09 12.461. Nigeria 3.53 3.78 3.81 3.88 3.78 38.85 41.57 45.72 43.41 44.58 11.00 10.99 12.00 11.20 11.802. Thailand 1.06 0.99 1.07 1.17 1.18 21.44 16.94 22.58 26.92 27.57 20.28 17.18 21.09 22.92 23.293. Brazil 1.75 1.90 1.90 1.89 1.84 23.93 25.87 26.64 26.54 25.88 13.63 13.61 14.05 14.01 14.074. Indonesia 1.26 1.21 1.23 1.20 1.19 19.42 19.32 19.99 19.99 21.59 15.47 15.92 16.28 16.64 18.095. Congo 1.84 1.85 1.88 1.85 1.85 14.95 14.97 14.99 15.00 15.02 8.11 8.11 7.98 8.11 8.116. Ghana 0.78 0.75 0.79 0.80 0.80 9.74 9.57 9.64 9.65 9.65 12.42 12.76 12.20 12.06 12.067. Viet Nam 0.39 0.43 0.48 0.50 0.56 5.82 6.72 7.78 8.19 9.40 14.98 15.78 16.38 16.53 16.918. India 0.22 0.24 0.24 0.26 0.27 5.95 7.46 7.85 8.23 9.05 27.04 30.50 32.11 32.22 33.559. Angola 0.68 0.75 0.76 0.76 0.76 8.59 8.61 8.81 8.84 8.84 12.56 11.50 11.64 11.63 11.6310.Tanzania 0.66 0.67 0.67 0.68 0.68 4.44 5.54 6.16 6.60 6.60 6.73 8.27 9.19 9.78 9.78
The Top 10 Cassava ProductionBased on year 2008
Source: Food and Agriculture Organization of the United Nations (FAO), 2009
Cassava and Starch Technology Research Unit
0
5
10
15
20
25
30
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
Pla
nta
tion
are
a (M
illi
on R
ai)
/P
rod
uct
ion
(M
illi
on t
ons)
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
Productivity (T
ons/Rai)
Plantation area (Million Rai) Production (MT) Productivity (ton/rai)
Cassava production in Thailand
Note : 1 hectare = 6.25 rai
Cassava and Starch Technology Research Unit
Goals 2008 2009 2010 2011
Plantation area (M Hectare) 1.2 1.2 1.2 1.2
Productivity (T/Hectare) 21.9 25.0 26.9 28.1
Total production (M Ton) 25.53 29.60 31.45 33.3
Use of cassava (M Ton)
Domestic 7.77 8.19 8.42 8.69
- Chips/pellets 2.31 2.52 2.63 2.73
- Starch 5.46 5.67 5.80 5.96
Export 15.96 20.16 21.42 22.05
- Pellets 4.20 3.36 3.36 3.15
- Chips 2.10 6.72 7.35 7.77
- Starch 9.66 10.08 10.71 11.13
Bioethanol 1.83 1.25 1.61 2.56
or ethanol (ML/day)* 0.85 0.58 0.75 1.19
Cassava plan (2008 – 2011)
Source: Office of Agricultural Economics, 2008
*1 ton cassava produces 167L of ethanol with 360 day/year production
Cassava and Starch Technology Research Unit
Sugar crops Starch crops Agricultural residues
Sugar SugarSugar
Fermentation
Cooking / Enzyme hydrolysis
Lignocellulosic materialsStarch
Enzyme hydrolysis
Pretreatment
1st Generation 2nd Generation
Cassava and Starch Technology Research Unit
Fermentator
Purification Lactic acid Lactide PLA
Production process of polylactic acid (PLA)
Enzyme hydrolysis
Gypsum
Fermentator
Mash Distillation Dehydration Anhydrous ethanol
Production process of ethanol
Enzyme hydrolysis
Catalyst
Production process of polyhydroxyalkanoate (PHAs)
Cassava and Starch Technology Research UnitFermentator
Extraction/Purification
PHAsEnzyme hydrolysis
Beverage industry
EthanolEthanol
(CH3CH2OH)
Cosmetic industry
Chemical industry- green solvents
Chemical feedstock- ethyl lactate- acetic acid- ethyl acetate
Pharmaceutical industry
Liquid fuels
Cassava and Starch Technology Research Unit
Food industry- acidulants- preservatives- flavours- pH regulators- improving microbial quality
Lactic acidLactic acid
(CH3CHOHCOOH)
Cosmetic industry- moisturizers- skin-lightening agents- pH regulators- anti-acne agents- humectants- anti-tartar agents
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
Pharmaceutical industry- dialysis solution- mineral preparations- tablettings- prostheses- surgical sutures
Biodegradable plastics
Cassava and Starch Technology Research Unit
– Plastics which include
more than 25% biomass
origin raw materials
Bioplastics
Biomass-based Biodegradable
– Plastics which are broken
down by microorganisms
into carbon dioxide and water
and the biodegradability must
be higher than 60% by interna
tional analysis method
Bioplastics
Source: Japan BioPlastics Association (JBPA)
– Biodegradability notconcerned
– Raw material origin not concerned
Cassava and Starch Technology Research Unit
Petroleum-based Bio-based
Biodegradable*/ Compostable**
Non-Biodegradable / Non-Compostable
Conventional plastic
Least Earth Friendly
*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).
PVCPSBio-PE
Bio-PET Bio-PA
PBAT
Modified PETPBS
PCL PBSA
ABS
PP
PET
HDPELDPE
Earth Friendly
PLA PHA PHBV
Starch-based polymer
Cassava and Starch Technology Research Unit
Raw material
First generation feedstock
Second generation feedstock
Sugar crop: sugar cane, beets, sweet sorghum
Starch crop: corn, wheat, potato, rice, cassava
LignocellulosicCellulose
Hemicellulose
Lignin
Processing
FermentationPpolymerization
Monomers(Lactic acid, succinic acid)
PolymersPolylactic acid, PBAT
Masterbatch
Applications
Processing additive Plasticizers, LubricantsProduct additive Water, Heat, Light, Wear, Impact, Pesticide resistance, etc. Color, Titanium dioxide, Carbon black, fiber reinforcement; cellulose, etc.Filler Calcium carbonate Starch Cellulose
Injection moldingCompression moldingExtrusionFilm blowingThermoforming
Plastic bag, Food container, Mulch film
Disposable, Semi-durable & Durable
Use of starch in bioplastic
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
Cassava and Starch Technology Research Unit
Starch
Cassava
Fermentation
Bio-Polypropylene
Lactic acid
Bio-Polyethylene(Green Polyethylene 2011)
PHB
Promise of cassava use as sugar in bioplastics
PLA
Ethanol
Sugar
Cassava and Starch Technology Research Unit
Promise of cassava use as polymer in bioplastic
Starch
As monomer(GLUCOSE)
As polymer(STARCH)
Enzyme hydrolysis
Microbial fermentation
Monomer Polymer
Polymerization
Starch / polymer blends
Other polymers - Natural: rubber, cellulose- Synthetic: PBAT, PBS
Starch materials- Foam- Film- Adhesive- Superabsorbent
- Granular
- TPS
Cassava and Starch Technology Research UnitStarch graft copolymers
Poly (lactic acid) - PLA
Starch (1.8 tons)
Cassava root (7.2 Tons)
PLA (1 ton)
L-lactic acid (1.3 tons)
Cassava and Starch Technology Research Unit
Value50,361 million baht
Value Added
1.31 fold
65,964 million baht
Value Added1.5 fold
75,752 million baht
40.4 %
Thai Root Production29.6 million tons (1.7 baht/kg)
50,361 million baht
Pellets Export 0.33 million ton (4.4 baht/kg)
1,458 million baht
Dried ChipLocal 1.11 million ton (4.0 baht/kg)Export 4.02 ล้�านตั�น (4.71 baht/kg)
23,389 million baht
Native StarchLocal 1.29 ล้�านตั�น (9.0 baht/kg)
Export 2.52 ล้�านตั�น (11.71 baht/kg)41,105 million baht
Animal Feed(Chip/Pallet)
24,373 million baht
Ethanol0.12 million liter (20 baht/liter)
2,429 million baht
Modified starch0.12 million tons (14.5 baht/kg)
1,740 million baht
Sweeteners0.5 million tons (16.0 baht/kg)
8,000 million baht
Export cassava starch
2.52 million tons (11.71 baht/kg)29,495 million baht
Other products(Food industry, MSG, Paper)
9,715million baht
Local consumption cassava starch
1.29 million tons (9.0 baht/kg)11,610 million baht
2.5 % 57.1 %
Native starch 0.4 million tons (Expected)
Native starch 0.5million tons
Native starch 0.6 million tons
Native starch 0.12million tons
Cassava chips 0.53 million tons (Expected)
Cassava and Starch Technology Research Unit
Value added
1.8 fold
91,071 million baht
Value added
1.96 fold
98,532 million baht
PLA0.2 million tons (100 baht/kg)
20,000 million baht
(modified from Gould et al., 1990)
Granular starch Thermoplastic Starch (TPS)
Granular starchOther polymers
Starch / polymer blend
Additives / plasticizers
Thermoplastic starch (TPS)
TPS and Melted Polymer
Granular starch
Other polymers
Starch / polymer blend
Use of starch in polymer blends
- 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 properties as well as processing,
additives
Cassava and Starch Technology Research Unit
Some characteristics of starch granules from different botanical sources
Properties Waxy corn Normal corn
High amylose
Corn
Wheat Potato Rice Cassava
Granule shape Round, polygonal
Round, polygona
l
Long, irregular
Round, lenticular
Oval Polygonal Oval, truncated
Granule size (range in microns)
3-26 2-30 4-22 1-45 5-100 2-13 4-35
Source: Swinkels (1998); Ozturk et al. (2009); Corn Refiners Association, Inc; Jane (2000); n.a. = not available
Cassava and Starch Technology Research Unit
Functional properties Source of starch
Cassava Corn
Flow behavior index (n)
Heat stability index (HIS)1
Acid stability index (ASI)2
Shear stability index (SSI)3
Least concentration for gelation (% starch w/v)4
0.363
0.73
0.74
0.11
8.00
0.381
1.25
0.97
0.10
6.00
Peak viscosity (cP)5
Gelatinization temperature (C)5
1769
66.20
2609.00
78.25
Hardness (N)6
Brittleness (N)6
Adhesiveness (N mm)6
7.20 ± 0.36
3.75 ± 0.13
-0.49 ± 0.04
12.04 ± 1.69
6.52 ± 0.11
-0.55 ± 0.06
Some characteristics of corn and cassava starches
Source: Mishra and Rai, 2006.
1121C, 15 min with 500s-1;2pH 3;31000 s-1;44C overnight; 3g dry starch in 25g water; 620% (w/w)
Cassava and Starch Technology Research Unit
Modification of starches
• Esterification• Etherification• Crosslinking• Grafting• Dextrinization• Thinning• Oxidation• Radiation• Hydro-thermal• Enzyme
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
Improved functionality
Cassava and Starch Technology Research Unit
Cassava and Starch Technology Research Unit
Cassava-based thermoplastic starch / Cassava-based materials
Cassava and Starch Technology Research Unit
Corn-based Cassava-based
Cassava and Starch Technology Research Unit
Cassava and Starch Technology Research Unit
Cassava and Starch Technology Research Unit
Fiber diameter : 200 – 2,000 nanometerStarch in total solid : 5 – 40% by weight
Human hair ~ 10 micrometer ~ 10,000 nanometer 1/50 – 1/5 of human hair
Research and Development
Cassava and Starch Technology Research Unit
Griffin et.al. introduced granular starch pellet as particulate filler in PEOtey et.al. developed gelatinized starch plastic system
Forms of starch:
granular starch, modified starch, and TPS
Composite materials :
PLA, PVA, LDPE, PBAT, cellulose, and lignin
Additives :
Flame retartdant, nanoparticle, impact resistant
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
Cassava and Starch Technology Research Unit
CASSAVA BIOREFINERY
Cassava and Starch Technology Research Unit
Cassava roots
Starch Chips
Pulp
Peel / Stem
Cassava plants
LeavesStalk
BiotechnologicalConversion
ChemicalConversion
Decomposition
Gasification
Lig
nin
Hem
icel
lulo
se
Cel
lulo
se
Syn
gas
PH
B
Met
han
ol
Glu
cosa
min
e
Sor
bit
ol
Starch esters
Bio-plastic
Co-and mix-polymers
Co-extrusion
Extrusion
Plasticization
Direct use
DryingIn-field fertilizer
Animal feed
Ensiling/silage
Hyd
roge
nat
ion
Red
-An
imat
ion
Est
erif
icat
ion
Eth
er
form
atio
n
Glucose
Ethanol
Fermentation
Combustion electricity
Energy
Starch extraction
Starch ethers
Thank you for your attention
Cassava and Starch Technology Research Unit