Promise of cassava in biorefinery

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


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


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


Biorefinery VS. Petroleum

refinery Alcohols

Organic acids

Nitrogenous compounds

Sugar and derivatives

Phenol, Furan

Fatty acid

Syngas

Etc.


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


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


(biodegradable)


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


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


Biomass1. Agricultural crops

2. Agricultural residues

3. Wood chips and residues

4. Waste streams / by-products from household and industry


http://images.google.co.th/imgres?imgurl=http://www.biosmartpackaging.com/sitebuilder/images/bagasse-pulp-342x228.jpg&imgrefurl=http://www.biosmartpackaging.com/Biodegradable_Materials.html&usg=__MnxKIkMAyPNKcu2wmhFydOIIswY=&h=228&w=342&sz=14&hl=th&start=3&itbs=1&tbnid=GLykIqqBT51YgM:&tbnh=80&tbnw=120&prev=/images?q=bagasses&hl=th&sa=G&gbv=2&tbs=isch:1

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


Potential feedstock in ThailandPotential feedstock in Thailand


SugarcaneSugarcane


CassavaCassava


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


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: 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


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


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


Sugar crops Starch crops Agricultural residues

Sugar SugarSugar

Fermentation

Cooking / Enzyme hydrolysis

Lignocellulosic materialsStarch

Enzyme hydrolysis

Pretreatment

1st Generation 2nd Generation


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


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


– 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


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


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


Promise of cassava in Thai bioplastics

Starch

- Use as monomer, i.e. glucose for microbial fermentation

- Use as polymer


Starch

Cassava

Fermentation

Bio-Polypropylene

Lactic acid

Bio-Polyethylene(Green Polyethylene 2011)

PHB

Promise of cassava use as sugar in bioplastics

PLA

Ethanol

Sugar


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)


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)


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


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


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)


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-based thermoplastic starch / Cassava-based materials


Corn-based Cassava-based



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


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


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 BIOREFINERY


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


Promise of cassava in biorefinery

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