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
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
Cassava and Starch Technology Research Unit
Petroleum refinery
Polyethylene
Ethylene
Ethylenoxide
Ethanol
Propylene
Propylenoxide
Acrylnitrile
C4-mixture
Benzol
Butadiene
Polystyrene
Nylon
Toluol
Polyurethane
Polyester
Xylol
Alkyd resin
Methanol
Synthetic gas
Ammonia
Primary chemicals
Cassava and Starch Technology Research Unit
Intermediate products
Biorefinery
Carbohydrates
(Sugars, Starches,
Cellulose)
Alcohols
Organic acids
Lignins
Nitrogenous compounds
Proteins
Sugar and derivatives
Lipids / Fats
Furan
Other substances
(Vitamins, Pigments,
Flavors etc.)
Etc.
Primary chemicals
Cassava and Starch Technology Research Unit
Intermediate products
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
Biorefinery
Biomass
Conversion
Bio-
Produces
Processes
Products
- Agricultural crops
- Bioprocess
- Fuels
- Agricultural residues
- Chemical process
- Power (electricity, heat)
- Forest biomass
- Physical process
- Chemicals
- Grasses
- Combination
- Materials
- Animal wastes
(Enzyme, Microbial
- Municipal solid waste
fermentation, Thermochemical, Pyrolysis,
Gastification, Steam
explosion etc.)
Cassava and Starch Technology Research Unit
Chemicals
Fuel/ Energy
- Bioethanol: Yeast fermentation
- Biodiesel: Transesterification
- Biogas: Biomethylation
- Organic acids
Lactic acid, succinic acids
citric acid, acetic acid,
- Nitrogenous compounds:
MSG, amino acids
Materials
- Biodegradable plastics
Polylactic acid (PLA),
Polyhydroxyalkanoates (PHAs)
Poly(butylene succinate) (PBS)
- Fiber
- Sugars & Derivatives
Xylitol, Sorbitol
1,3 propanediol (PDO)
- Furfural, hydroxy furfural
- Resins
- Foams
- Nanofiber
Cassava and Starch Technology Research Unit
1. Agricultural crops
Biomass
2. Agricultural residues
3. Wood chips and residues
4. Waste streams / by-products from household and industry
Cassava and Starch Technology Research Unit
Sugar-based biorefinery industry
First generation feedstock
- Sugar crop: sugar cane, beets, sweet sorghum
- Starch crop: corn, wheat, potato, rice, cassava
Second generation feedstock
Cellulose
Lignocellulosic
Hemicellulose
Lignin
Cassava and Starch Technology Research Unit
Potential feedstock in Thailand
Cassava and Starch Technology Research Unit
Sugarcane
Cassava and Starch Technology Research Unit
Cassava
Cassava and Starch Technology Research Unit
Agricultural practices and agronomic traits of major sugar crops
Parameter
Sugarcane
Cassava
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
Grow well in loamy soil
Grow well in sandy loams and/or loamy
sands
Requires water throughout the year /
36,000
Less water requirement; less than 1,000
mm/year
Greater fertilizer requirement
Little fertilizer requirement
Require good management
Less pest and disease; easy management
Labor intensive
December – March
Manual and labor intensive
All year round
70
25
8-15
30
11. Sugar/starch yield (tons/ha)
5.6-10.5
7.5
12. Other biomass
Leaves
Leaves, Stem
1. Crop duration
4. Soil requirement
5. Water management/
Requirement (m/ha)
6. Fertilizer input
7. Crop management
8. Harvesting
9. Feedstock yield (tons/ha)
10. Sugar/ starch content
(% by weight, wet basis)
Cassava and Starch Technology Research Unit
Chemical composition of harvested agricultural produces from various starch crops
Chemical composition (%wet basis)1
Starch Crops
Moisture
Protein
Lipid
Crude fiber
Ash
Carbohydrate
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)
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)
Corn grains2
Cassava roots6
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
Cassava and Starch Technology Research Unit
Cassava: Harvested area, production and yield of major countries 2004-2008
Country
Rank*
World
1. Nigeria
2. Thailand
3. Brazil
4. Indonesia
5. Congo
6. Ghana
7. Viet Nam
8. India
9. Angola
10.Tanzania
2004
18.00
3.53
1.06
1.75
1.26
1.84
0.78
0.39
0.22
0.68
0.66
Harvested area (million ha)
2005
2006
2007
18.47
18.34
18.55
3.78
3.81
3.88
0.99
1.07
1.17
1.90
1.90
1.89
1.21
1.23
1.20
1.85
1.88
1.85
0.75
0.79
0.80
0.43
0.48
0.50
0.24
0.24
0.26
0.75
0.76
0.76
0.67
0.67
0.68
2008
18.70
3.78
1.18
1.84
1.19
1.85
0.80
0.56
0.27
0.76
0.68
2004
203.11
38.85
21.44
23.93
19.42
14.95
9.74
5.82
5.95
8.59
4.44
Production (million tons)
2005
2006
2007
207.09 222.29 224.13
41.57
45.72
43.41
16.94
22.58
26.92
25.87
26.64
26.54
19.32
19.99
19.99
14.97
14.99
15.00
9.57
9.64
9.65
6.72
7.78
8.19
7.46
7.85
8.23
8.61
8.81
8.84
5.54
6.16
6.60
Source: Food and Agriculture Organization of the United Nations (FAO), 2009
2008
232.95
44.58
27.57
25.88
21.59
15.02
9.65
9.40
9.05
8.84
6.60
2004
11.29
11.00
20.28
13.63
15.47
8.11
12.42
14.98
27.04
12.56
6.73
Yield (tons/Ha)
2005
2006
2007
11.21
12.12
12.09
10.99
12.00
11.20
17.18
21.09
22.92
13.61
14.05
14.01
15.92
16.28
16.64
8.11
7.98
8.11
12.76
12.20
12.06
15.78
16.38
16.53
30.50
32.11
32.22
11.50
11.64
11.63
8.27
9.19
9.78
2008
12.46
11.80
23.29
14.07
18.09
8.11
12.06
16.91
33.55
11.63
9.78
The Top 10 Cassava Production
Based on year 2008
250
200
150
100
50
0
World
Nigeria
Thailand
Yield (tons/ha)
Brazil
Indonesia
Congo
Production (million tons)
Production…
Ghana
Viet Nam
India
Yield (tons/ha)
Angola
Cassava and Starch Technology Research Unit
Tanzania
Cassava production in Thailand
4.00
3.50
25
3.00
20
2.50
15
2.00
1.50
10
1.00
5
Productivity (Tons/Rai)
Plantation area (Million Rai) /
Production (Million tons)
30
0.50
5
6
7
8
9
0
1
2
3
4
5
6
7
199
199
199
199
200
200
200
200
200
200
200
200
0.00
199
0
Plantation area (Million Rai)
Production (MT)
Note : 1 hectare = 6.25 rai
Cassava and Starch Technology Research Unit
Productivity (ton/rai)
Cassava plan (2008 – 2011)
Goals
2009
2008
Plantation area (M Hectare)
2010
2011
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
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
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
0.58
0.75
1.19
Use of cassava (M Ton)
Domestic
Export
or ethanol (ML/day)*
0.85
*1 ton cassava produces 167L of ethanol with 360 day/year production
Source: Office of Agricultural Economics, 2008
Cassava and Starch Technology Research Unit
1st Generation
Sugar crops
2nd Generation
Starch crops
Starch
Agricultural residues
Lignocellulosic materials
Pretreatment
Cooking / Enzyme
hydrolysis
Enzyme hydrolysis
Sugar
Sugar
Fermentation
Cassava and Starch Technology Research Unit
Sugar
Production process of ethanol
Mash
Enzyme hydrolysis
Distillation
Dehydration
Anhydrous
ethanol
Fermentator
Production process of polylactic acid (PLA)
Catalyst
Gypsum
Enzyme hydrolysis
Purification
Lactic acid
Fermentator
Production process of polyhydroxyalkanoate (PHAs)
Enzyme hydrolysis
Extraction/
Purification
PHAs
Cassava and Starch Technology Research Unit
Fermentator
Lactide
PLA
Liquid fuels
Beverage industry
Cosmetic industry
Ethanol
Chemical industry
- green solvents
(CH3CH2OH)
Chemical feedstock
Pharmaceutical
industry
- ethyl lactate
- acetic acid
- ethyl acetate
Cassava and Starch Technology Research Unit
Food industry
- acidulants
- preservatives
- flavours
- pH regulators
- improving microbial
quality
Cosmetic industry
- moisturizers
- skin-lightening agents
- pH regulators
- anti-acne agents
- humectants
- anti-tartar agents
Lactic acid
(CH3CHOHCOOH)
Chemical industry
Chemical feedstock
- descaling agents
- pH regulators
- neutralizers
- chiral intermediates
- green solvents
- cleaning agents
- propylene oxide
Biodegradable
- acetaldehyde
plastics
- propanoic acid
- ethyl lactate
- poly (lactic acid)
- dilactide
Pharmaceutical
industry
- dialysis solution
- mineral preparations
- tablettings
- prostheses
- surgical sutures
Cassava and Starch Technology Research Unit
Bioplastics
Bioplastics
Biomass-based
– Plastics which include
more than 25% biomass
origin raw materials
– Biodegradability not
concerned
Biodegradable
– Plastics which are broken
down by microorganisms
into carbon dioxide and water
and the biodegradability must
be higher than 60% by
international analysis method
– Raw material origin
not concerned
Source: Japan BioPlastics Association (JBPA)
Cassava and Starch Technology Research Unit
Biodegradable*
/ Compostable**
PBAT
PBS
PCL
PBSA
Modified PET
Earth Friendly
PLA
PHA
PHBV
Starch-based polymer
Petroleum-based
Bio-based
Conventional plastic
PET
PP
ABS
LDPE
PS
Bio-PE
PVC
Bio-PET
HDPE
Bio-PA
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).
Cassava and Starch Technology Research Unit
Use of starch in bioplastic
Raw material
Processing
First generation feedstock
Sugar crop: sugar cane, beets, sweet sorghum
Starch crop: corn, wheat, potato, rice, cassava
Second generation feedstock
Lignocellulosic
Cellulose
Hemicellulose
Lignin
Applications
Fermentation
Ppolymerization
Monomers
(Lactic acid, succinic acid)
Polymers
Polylactic acid, PBAT
Disposable, Semi-durable & Durable
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
Masterbatch
Cassava and Starch Technology Research Unit
Injection molding
Compression molding
Extrusion
Film blowing
Thermoforming
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
Promise of cassava use as sugar in bioplastics
Cassava
Starch
Sugar
Fermentation
Ethanol
PHB
Bio-Polyethylene
(Green Polyethylene 2011)
Lactic acid
Bio-Polypropylene
Cassava and Starch Technology Research Unit
PLA
Promise of cassava use as polymer in bioplastic
Starch
Enzyme hydrolysis
As monomer
(GLUCOSE)
As polymer
(STARCH)
Microbial fermentation
- Granular
- TPS
Monomer
Polymer
Polymerization
Starch / polymer blends
Other polymers
- Natural: rubber, cellulose
- Synthetic: PBAT, PBS
Starch materials
- Foam
- Film
- Adhesive
- Superabsorbent
Starch graft copolymers
Cassava and Starch Technology Research Unit
Poly (lactic acid) - PLA
Cassava root (7.2 Tons)
Starch (1.8 tons)
L-lactic acid (1.3 tons)
PLA (1 ton)
Cassava and Starch Technology Research Unit
Thai Root Production
Value
50,361 million baht
29.6 million tons (1.7 baht/kg)
50,361 million baht
40.4 %
Value
Added
1.31 fold
57.1 %
2.5 %
Dried Chip
Native Starch
Pellets
Local 1.11 million ton (4.0 baht/kg)
Export 4.02 ล้านตัน (4.71 baht/kg)
23,389 million baht
Local 1.29 ล้านตัน (9.0 baht/kg)
Export 2.52 ล้านตัน (11.71 baht/kg)
41,105 million baht
Export 0.33 million ton (4.4 baht/kg)
1,458 million baht
65,964 million baht
Value
Added
1.5 fold
75,752 million baht
Ethanol
Animal Feed
0.12 million liter (20 baht/liter)
2,429 million baht
(Chip/Pallet)
24,373 million baht
Local consumption
cassava starch
Export
cassava starch
1.29 million tons (9.0 baht/kg)
11,610 million baht
2.52 million tons (11.71 baht/kg)
29,495 million baht
Native starch
0.6 million tons
Native starch
0.5million tons
Native starch
0.12million tons
Modified starch
Sweeteners
Other products
0.12 million tons (14.5 baht/kg)
1,740 million baht
0.5 million tons (16.0 baht/kg)
8,000 million baht
(Food industry, MSG, Paper)
9,715million baht
Cassava chips 0.53 million tons (Expected)
Value
added
1.96 fold
98,532 million baht
Native starch 0.4 million tons (Expected)
Value
added
1.8 fold
PLA
0.2 million tons (100 baht/kg)
20,000 million baht
91,071 million baht
Cassava and Starch Technology Research Unit
Use of starch in polymer blends
Granular starch
Thermoplastic starch
(TPS)
Other polymers
Granular starch
Additives / plasticizers
TPS and Melted Polymer
Starch / polymer blend
Other polymers
Starch / polymer blend
Granular starch
- 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
Thermoplastic Starch (TPS)
- 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
(modified from Gould et al., 1990)
Cassava and Starch Technology Research Unit
Some characteristics of starch granules from different botanical sources
Properties
Granule shape
Granule size
(range in microns)
Waxy corn
Normal
corn
High
amylose
Corn
Wheat
Potato
Rice
Cassava
Round,
polygonal
Round,
polygona
l
Long,
irregular
Round,
lenticular
Oval
Polygonal
Oval,
truncated
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
Some characteristics of corn and cassava starches
Functional properties
Source of starch
Cassava
Corn
Flow behavior index (n)
0.363
0.381
Heat stability index (HIS)1
0.73
1.25
Acid stability index (ASI)2
0.74
0.97
Shear stability index (SSI)3
0.11
0.10
Least concentration for gelation (% starch w/v)4
8.00
6.00
Peak viscosity (cP)5
1769
2609.00
Gelatinization temperature (C)5
66.20
78.25
Hardness (N)6
7.20 ± 0.36
12.04 ± 1.69
Brittleness (N)6
3.75 ± 0.13
6.52 ± 0.11
Adhesiveness (N mm)6
-0.49 ± 0.04
-0.55 ± 0.06
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.
Cassava and Starch Technology Research Unit
Modification of starches
Technology tools
• Esterification
• Etherification
• Crosslinking
• Grafting
• Dextrinization
• Thinning
• Oxidation
• Radiation
• Hydro-thermal
• Enzyme
Improved functionality
• 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
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
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
Cassava and Starch Technology Research Unit
Research and Development
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
Griffin et.al. introduced granular starch pellet as particulate filler in PE
Otey et.al. developed gelatinized starch plastic system
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 plants
Stalk
Cassava roots
Leaves
Peel / Stem
Ensiling/silage
In-field fertilizer
Pulp
Starch
extraction
Drying
Starch
Chips
Animal feed
Combustion electricity
Biotechnological
Conversion
Energy
Chemical
Conversion
Extrusion
PHB
Methanol
Syngas
Cellulose
Hemicellulose
Lignin
Ether
formation
Co-extrusion
Esterification
Ethanol
Red-Animation
Fermentation
Glucosamine
Decomposition
Sorbitol
Glucose
Hydrogenation
Gasification
Direct use
Plasticization
Bio-plastic
Co-and mixpolymers
Starch esters
Starch ethers
Cassava and Starch Technology Research Unit
Thank you for your attention
Cassava and Starch Technology Research Unit