Author: Klanarong Sriroth1, 2 Kuakoon Piyachomwan3, Kunruedee

Sangseethong3 and Christopher Oates4

Title: Modification of cassava starch

Abstract
Cassava (Manihot esculenta Crantz) is an important food crop in many
tropical countries in Africa, South America and Asia. However, in Thailand, this crop
has been well recognized as more than a subsistence crop. It is important
commercially as the raw material for a large and complex industrial system that has a
significant impact to the country’s economics. The roots of this crop contain high a
starch content and approximately half of the total roots produced (20 million tons) are
used for the starch industry. Cassava starch has many remarkable characteristics
including high paste viscosity, high paste clarity and high freeze-thaw stability, which
are advantageous to many industries. In particular, the native starch with high purity
can be readily modified by physical, chemical and enzyme process to many
diversified products to improve the starch functionality and, consequently, encourage
more industrial application. This paper aims to describe the unique modification of
cassava starch produced at the industrial level in Thailand with respect to
technological aspect and product quality.

1
Department of Biotechnology, Faculty of Agro- Industry, Kasetsart University, Bangkok, Thailand
2
Kasetsart Agricultural and Agro-Industrial Product Improvement Institute, Kasetsart University,
Bangkok, Thailand
3
National Center for Genetic Engineering and Biotechnology, Bangkok, Thailand
4
Agro Food Resources (Thailand) Co., Ltd., Bangkok, Thailand

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
1
1. Introduction
Cassava (Manihot esculenta) is an important food crop in tropical countries
such as Brazil, Nigeria, Indonesia and Thailand. The roots of cassava are rich in
starch and consumed as human food or animal feed. Only a small amount of roots is
converted into other industrial products. Thailand is the only country where most of
the roots are processed into chips, pellets and starch. Against the total world root
production of 175 million tons (Table 1), Thailand produces about 18 million tons.
Ten million tons are converted to starch, producing approximately 2 million tons
starch/year, and the rest to chips and pellets. As the leader of cassava starch
production (Figure 1), Thailand is also the only country where modified starches from
cassava are produced in large scale. Around 50% of the starch (native and modified)
are employed locally in the food and non-food industries, the remainder is exported.
This commodity generates significant revenue for the country (Table 2) and the future
is promising. Growth of the starch industry sector is, in part, a substantial driving
force that has generated large-scale cassava planting for commercial purpose in
Thailand. From the experience in Thailand, this paper describes the unique
modification of cassava starch.

Table 1 World production of cassava roots in 2001

Country Volume (million tons)

Nigeria 33,854,000
Brazil 24,481,356
Thailand 18,283,000
Congo 15,959,000
Indonesia 15,800,000
Ghana 7,845,440
Tanzania 5,757,968
India 5,800,000
Mozambique 5,361,974
China 3,750,900
Other 38,723,751
Total 175,617,389
Source: FAOSTAT, 2001.

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
2
 2000
Annual starch production ('000 tonnes)

1500

1000

500

0
Thailand Brazil Indonesia India China Vietnam Malaysia Philippines

Figure 1 Cassava starch production in various countries.

Source: Ostertag, 1996; The Thai Tapioca Flour Industries Trade
Association, 2001.

Table 2 Export volume and value of Thai cassava starch

Cassava starch Volume (tons) Value (million Baht*)

1999 2000 2001 1999 2000 2001
Native starch 699,175 1,044,087 724,393 4,817.43 6,148.86 5,241.89
Modified starch 331,604 365,571 344,738 5,606.95 6,257.29 6,063.75
Sago pearl 15,508 15,470 14,455 164.64 150.14 150.49
Total 1,046,287 1,425,128 1,083,586 10,588.84 12,556.29 11,456.13
*1 USD = 45 Baht
Source: The Thai Tapioca Flour Industries Trade Association, 2001

2. Modification
2.1 Native Starch
The term “native starch” is defined as the product extracted from cassava
roots, which is called “starch” – not “flour” by the modern separation process (Sriroth
et al., 2000). The standard for starch content in native cassava starches is not less than

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
3
96% (dry basis). For modification purposes, native starch of the specification
summarized in Table 2 is used.

Table 3 Standard Specification of native cassava starch for modification purpose

Property Specification
Moisture content (% maximum) 13 %
Ash (% maximum) 0.2 %
Fiber (cm3 per 50g wet starch, maximum) 0.2
pH 5.0 to 7.0
Whiteness (Kett scale, minimum) 90
Viscosity (Barbender Unit, minimum) 600
Sulfur dioxide content (ppm, maximum) 100
Residue (ppm, maximum) 300

2.2 Modification of cassava starch in Thailand

The starch modification sector is one of the most important industries in
Thailand. This industry began as the production technology of cassava starch
developed from small- to large-scale and starch quality improved. One of the main
driving forces was the high market demand; both domestically and internationally, for
the diversified cassava-based products produced by the modification technology. The
modified cassava starch and derivatives currently produced at the commercial scale
can be categorized based on the technology approach as summarized in Figure 2.

2.2.1 Physical modification

This group of modified starches involves the treatment of cassava starch by
physical means such as shear force, blending and thermal treatment. A combination
of heat treatment and shear force has been used to produce many extruded products
and snacks. The well-known products for cassava starch are alpha starch and heat-
moisture treated starch obtained by a thermal process.

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
4
 Thai cassava starch

Physically modified starch Chemically modified starch Hydrolyzed Starch & Derivatives
Pregelatinized starch Acid thinned starch Maltodextrin
Heat-moisture treated starch Dextrinized starch Sweeteners
Sago pearl or tapioca pearl Oxidized starch Glucose
Starch ether Fructose
Hydroxy-propyl starch Polyols
Starch ester Sorbitol
Starch Octenylsuccinate Mannitol
Acetylated starch Amino acid
Phosphate mono-ester starch Glutamate
Cross-linked starch Lysine
Di-starch phosphate Organic acid
Dual – modification Citric acid
Hydroxy – propyl distarch phosphate
Acetylated distarch adipate
Acetylated distarch phosphate

Figure 2 Modified cassava starch and derivatives currently produced at commercial scale in Thailand.

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
5
2.2.1.1 Alpha starch
Alpha starch or pregelatinized starch began to be a major industry in the late
1980’s during the eel-farming boom when farms required a cold water soluble binder.
Alpha starch from cassava gives specific properties such as high transparency,
absence of foreign odors, good color carrier properties and high viscosity. The total
production capacity for all alpha starch in Thailand is about 50,000 tons/year. The
manufacturing process involves drying of 30 – 40 % (dry solid) cassava starch slurry
on a roller drum drier heated to 160-170°C by direct steam (Figure 3). Presently
alpha starch is produced as food grade, and is used in many industries (Table 3).

Table 4 Specification of food-grade alpha starch produced from Thai cassava starch

Property Specification
Moisture content (% maximum) 13
PH 4.5-7.0
Viscosity (Barbender Unit*, minimum) 800**
Ash (% maximum) 0.2
3
Pulp (cm , maximum) 0.2
Cyanide (ppm) nil
Residues (ppm, maximum) 300
Whiteness (Kett scale, minimum) 90
Sulfur dioxide content (ppm, maximum) 30
*Using 6% starch (dry basis)
**Upon the customer’s request and application

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
6
 Starch

Water + additives

Starch slurry
(19.5 - 20 oB'e, pH 6-7)

Storage tank

Drum Dryer
Steam
(160 - 170 oC)

Rotary hopper tank

Cyclone

Sieve

Packaging

Figure 3 Alpha starch process.

2.2.1.2 Heat-moisture treated starch

Heat-moisture treated starch is the oldest physically modified cassava starch. It
had been manufactured in early time since the settling pond was used for separation of
starch cake. The collected starch cake from the pond containing about 50% moisture
content was used as the starting material for making heat-moisture treated starch.
After being dried overnight on a hot floor (50 to 80°C), the dried starch was ground,
sieved and packed. The product was accepted as flour with special name called Tao
starch, not cassava starch. This starch is preferentially used as the product improver
for many Thai desserts and food recipes replacing the traditional starch extracted from
Tacca pinnatifida (Tao Yai Mom) tubers, which is rare and more expensive than
cassava starch. At present, all starch factories operate the modern separation
technique instead of settling. The current manufacturing process, then, starts with

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
7
soaking dried cassava starch overnight in ceramic or cement ponds. The moisture
content of starch cake is about 50 % and wet starch is then dried on the hot floor. The
produced starch has a remarkably different pasting profile from the native one (Figure
4).

Figure 4 Paste viscosity profiles as determined by a Rapid Visco Analyzer (using

3g starch of 14% moisture content in 25g of distilled water) of heat-
moisture treated (HT) and native cassava starches.

2.2.1.3 Sago pearl or tapioca peal

Sago pearl is one of the unique products produced from cassava starch in
Thailand. Originally, this pearl was made from starch obtained from the stem of sago
(Metroxylon spp.) palms which occur naturally only in the Southern part of Thailand.
Due to the scarcity of sago starch, the technology of making sago pearls from cassava
starch was developed and the product, called tapioca pearls, is used in some food
products. The process for producing sago pearl involves heat-moisture treatment and a
mechanical process. Similar to heat-moisture treatment, the starch is wetted overnight
in ceramic or cement ponds to reach 50% moisture content. Wet starch is shaped to
sphere-like by shaking continuously and the products subjected to dry heat process at
250 – 300°C. The pearls are cooled before being subjected to another drying process
at a lower temperature (50-80°C) on the hot floor. The pearls are then graded and
packed. When cooked, the pearl has a very unique characteristic as the pearl’s surface

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
8
is soft and transparent but inside is hard and opaque. Nowadays, the amount of starch
used in the sago industry is about 60,000 tons per year, accounting for 6% of total
domestic cassava starch consumption.

2.2.2 Chemical Modification

This group of products is prepared by chemical reaction. The most popular are
oxidized starch and acid-modified starch for paper industry. The production of
hydroxy – ethylated starch, cationic starch and amphoteric starch from cassava for
paper industry is prepared only in a small scale. Starch acetate and phosphate are the
most produced products for food industry.

2.2.2.1 Oxidized starch

Oxidized or chlorinated starch is one of the biggest-volume products produced
from cassava starch. The preparation of oxidized starch is normally accomplished by
the reaction of starch with sodium hypochlorite (NaOCl) under alkaline conditions.
Oxidized starch is used at the size press as a surface sizing on wide range of uncoated
free sheets to strengthen the paper surface. Traditionally, it is applied at 40 to 45 tons
per ton of paper (Tupper, 1995). Based on estimated paper consumption in Asian
countries, an additional demand of about 240,000 tons of oxidized starch is expected
each year (Tupper 1995).
Cassava starch, as a dominant source of starch in Asian countries, possesses a
strong film, clear paste, good water holding properties and stable viscosity and should
be the most suitable material for paper industry in this region.
Characteristics of oxidized cassava starch are influenced by oxidation
conditions. Compared to the strong oxidized starches, the mild oxidized starch
(prepared by 1,000 ppm active chlorine at pH 10.5) produces a stable high paste
viscosity, which is called – Stabilized high viscosity starch (Kettlitz and Coppin,
2001) (Figure 5).

2.2.2.2 Acid modified starch

Acid modified starch is also a well-known product in many Thai cassava
starch factories. This product is normally prepared during the production of native
starch. The preparation involves the addition of acid (usually hydrochloric acid) to the
starch slurry (≈ 20°Be) at the temperature below the gelatinization temperature. After

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
9
the reaction is finished and neutralized with soda ash, the starch slurry is concentrated,
dewatered and dried. The acid modified starch should give the viscosity less than 30
cPs and pH about 5.0-6.0.
A main characteristic of acid modified cassava starch is the low tendency of
the starch to retrograde compared to other starches. The handling of acid modified
cassava starch under 70 – 85o C does not create any film-forming problem in storage
tanks.

Figure 5 Paste viscosity as determined by a Rapid Visco Analyzer (using 3g starch

of 14% moisture content in 25g of distilled water) of oxidized cassava
starches prepared by using different levels of sodium hypochlorite (0 to
10,000 ppm).

2.2.2.3 Starch acetate

Starch acetate is a representative of modified cassava starches for the food
industry. The high volume of consumption is in food seasoning and sauce industry.
The normal preparation process of starch acetate is the reaction of vinyl acetate

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
10
monomer (max 7.5 % of starch dry weight) to cassava starch under an alkaline
aqueous suspension. The standard allowance of acetyl groups in modified starch for
food application is 2.5 % as the maximum level.

2.2.2.4 Other modified cassava starches for food products and their regulations
- Monostarch phosphate
Preparation: Orthophosphoric acid, Sodium orthophosphate, Sodium
tripolyphosphate
Product regulation: Phosphate (calculated as phosphorus) not more than
0.4 % (0.5% for potato and wheat starch)

- Distarch phosphate
Preparation: Sodium trimetaphosphate, Phosphorous oxychloride
Product regulation: Phosphate (calculated as Phosphorus) not more than
0.04 % (0.14 % for potato and wheat starch)

- Starch succinate
Preparation: Succinic oxide, Octenylsuccinic anhydride
Product regulation: Octenyl succinic group not more than 0.3 %

- Hydroxyl - propyl starch

Preparation: Propylene oxide (max 10 %)
Product regulation: Propylene chlorohydrin not more than 1 mg/kg and
hydroxy - propyl group not more than 7.0 %

- Hydroxy - propyl - distrach phosphate

Preparation: Sodium trimetaphoaphate, Phosphorous oxychloride and
propylene oxide (not more than 10 %)
Product regulation: Propylene chlorohydrin not more than 1 mg/ kg and
Hydroxy - propyl group more than 4.0 %

- Acetylated distrach phosphate

Preparation: Phosphorous oxychloride and vinyl acetate not more than
7.5 % (in case of acetic anhydride not more than 10%)

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
11
 Product regulation: Acetyl group not more than 2.5 %
Phosphate (calculated as phosphorous) not more than
0.04% (0.14% for potato and wheat starch)

2.2.3 Starch hydrolysate and derivatives

This industry sector consumes the biggest volume of cassava starch produced
in Thailand. The major product of this group is as a sweetener; important are glucose
and fructose syrup. Glucose syrup is further used as the starting material for other
industries; the biggest one is monosodium glutamate/ lysine (Table 4).

Table 5 Expected annual demand for cassava starch for the production of
sweeteners and MSG/lysine in Thailand.

Products Quantity of starch used Product yield

(tons/year) (kg/kg of starch)
High fructose (42% dry solid) 54,000 1.00
Glucose syrup 60,000 0.90-0.95
Dextrose monohydrate 20,000 1.75
Dextrose anhydrous 500 0.50
Sorbitol 30,000 1.20
MSG/Lysine 233,000 0.42
Source: Sriroth, 1998; The Thai Tapioca Flour Industries Trade Association, 2001

2.2.3.1 Sweeteners (glucose/fructose/sorbitol)

In Thailand, there are 14 factories manufacturing glucose syrup (two also
produce sorbitol) and two large international sorbitol producers (Ueno Co., Ltd.,
Japan and Lucky Chemical Co., Ltd., Korea). There are two factories producing high
fructose syrup (about 54,000 tons per year). All factories prefer to apply the enzyme
process for hydrolyzing starch and isomerizing glucose to produce glucose and
fructose syrup.

2.2.3.2 Monosodium glutamate (MSG) and lysine

Highest consumption of native cassava starch in Thailand is by the MSG (four
factories) and lysine (one factory) industries. Starch consumption for production of

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
12
these products is in the proportion of 80:20 by the MSG and lysine industries,
respectively. Production of commercial MSG in Thailand utilizes only two
carbohydrate sources for inoculation including molasses and cassava starch. To
produce one ton of MSG, factories need either about 2.4 tons of cassava starch or 7.0
tons of molasses.

2.2.3.3 Other starch hydrolysate and derivatives

- Citric acid
There are only two factories manufacturing citric acid in Thailand. One uses
cassava pulp from starch factories as the raw material (about 5-6 tons/day) for its solid
state (surface) fermentation. The other, recently established, uses cassava chips as the
raw material for its submerged fermentation process. About 40 tons of chips are
needed to produce 6 tons of citric acid per day.

- Maltodextrin
Maltodextrin produced from cassava starch in Thailand usually has the
dextrose equivalent value greater than 10 (DE = 10, 14 and 17). The production of
maltodextrin with DE < 10 is still limited to the low yield due to the filtration problem
caused by the retrogradation of starch hydrolysate prior to spray drying. The process
involves the hydrolysis of cooked starch with microbial enzymes and, when the
reaction is terminated, the hydrolysate is filtered and spray-dried. Significant
properties such as solubility, viscosity and water adsorption capacity, of cassava-
based maltodextrin are much more similar to corn-based than potato-based
maltodextrin (Figure 6).

3. Conclusion
Cassava can be more than a subsistence crop that contributes to the
sustainability of millions of farmers. With technology development, the high-starch
containing roots of this crop can be converted to starch, an important material for
other upstream industries of many value-added products by modification technology.

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
13
 35
30
Shear stress (dyn/cm2)
25
20
15
10
5
0
0 50 100 150 200 250 300 350
Shear rate (1/s)

Cassava (I) Cassava (II) Corn Potato

Figure 6 Shear rate and shear stress of maltodextrin DE 5 (20% solution at 25°C)
obtained from cassava starch prepared by two types of enzymes (I and II),
corn starch and potato starch.

4. Reference
1. FAOSTAT, 2001. http://www.fao.org
2. Kettlitz B. W., Coppin J.V.J.M: U.S. Pa. 6235894, 2001.
3. Ostertag C.F.: World production and marketing of starch. In: D. Dutour, G.M.
O’Berin and R. Best (Eds). Cassava Flour and Starch: Progress in Research
and Development. CIRAD/CIAT, Cali, Columbia. 1996, 105-120.
4. Sriroth K., Piyachomkwan K., Wanlapatit S., Oates C.G.: Starch/Starke, 52, 2000,
439-449.
5. Sriroth K.: Status of the Cassava-Industry Technology in Thailand, National Center
for Genetic Engineering and Biotechnology (BIOTEC), Thailand. 1998, 113 p.
(in Thai)
6. The Thai Tapioca Flour Industries Trade Association. 2001. Private
communication.
7. Tupper E.: The paper industry and starch applications. Proceeding of the
International Symposium on Cassava Starch and Starch Derivatives. Nanning,
Guangxi, China Nov 11-15, 1992, 1995, 37-41.

Paper presented at X International Starch Convention, 11-14 June 2002, Cracow, Poland.
14