Starch/Stärke 57 (2005) 71–78 DOI 10.1002/star.

200400351 71

Kuakoon Piyachomkwana Transformation and Balance of Cyanogenic

Sittichoke Wanlapatita
Sunee Chotineeranata
Klanarong Srirothb, c
a
Cassava and Starch Technology
Research Unit,
National Center for Genetic
Engineering and Biotechnology
(BIOTEC), Thailand
b
Dept. of Biotechnology,
Faculty of Agro-Industry,
Kasetsart University, Thailand
c
Kasetsart Agricultural
and Agro-Industrial Product
Improvement Institute,
Kasetsart University, Thailand
Compounds in the Cassava Starch Manufacturing
Process
The balance of total cyanogenic compounds and distribution of each compound
including bound cyanide, cyanohydrin and free cyanide were evaluated in a cassava
starch factory, having a production capacity around 100 t starch per day. The produc-
tion of starch began with transferring washed roots to the rasper, followed by a series
of extractors, separators, dewatering centrifuge and flash dryer, with an average water
consumption of 11.4 t per ton dry starch. The total amount of cyanogenic compounds
entering the process varied from 28 to 43 kg HCN equivalent per day, depending on the
root quality. In roots, 64% of bound cyanide was primarily found and it significantly
decreased to 22% after rasping whereas the cyanohydrin content increased from 34%
to 62%. Most of cyanogenic compounds, predominantly present as cyanohydrin (55 to
70%), was discharged in liquid and solid wastes, accounting for 92% and 5% of total
cyanide in roots, respectively. Only a negligible amount of cyanogenic compounds
remained in the starch products, having less than 2 mg HCN equivalent per kilogram
dry starch. Typically, water from the separators with 91% total cyanide content was
recycled to the root washer before being discharged as wastewater, whereas the liquid
from the coarse extractor (43% of total cyanide) was recycled to the rasper. This could
cause the accumulation of cyanogen in the process and, therefore, in the finished
products. With knowledge of the balance and transformation of cyanogens in starch
processing, it is possible to assure the quality of low-cyanide starch by modifying
starch process features such as water circulation and pH adjustment.

Keywords: Cassava starch; Cyanogenic compounds; Starch processing

1 Introduction
Many plants, at least 2,000 species grouped in 110 fami-
lies including cassava (Manihot esculenta Crantz) have the
ability to produce hydrogen cyanide (HCN) in vivo by the
cyanogenesis pathway. Typically, free HCN is not pro-
duced in the plant; indeed it is synthesized and accumu-
lated as cyanogenic glucosides or bound cyanide [1].

Research Paper
Cassava contains two types of cyanogenic glucosides,
namely linamarin and lotaustralin in a ratio of approxi-
mately 20: 1 [2]. When plant tissues are ruptured inten-
tionally or unintentionally, cyanogenic glucosides can be
hydrolyzed by linamarase, an endogenous enzyme being
found compartmentalized in plants, to liberate glucose Fig. 1. Degradation of linamarin, a major cyanogenic
and acid-stable acetone cyanohydrin compounds (Fig. 1) compound found in cassava root [1].
[3]. The cyanohydrin can further decompose sponta-
neously under neutral and alkaline conditions (pH . 5) to The contents of cyanogenic compounds in cassava roots
volatile hydrogen cyanide (free cyanide), which is rapidly are varied, depending on variety, harvest time, environ-
lost from the system due to its volatile nature [4, 5]. mental condition of growth and cultural practices [6–9].
Based on the cyanogenic contents in edible roots, cas-
sava can be classified into three classes, including low
Correspondence: Klanarong Sriroth, Dept. of Biotechnology,
toxic (or sweet type), medium toxic and high toxic (or
Faculty of Agro-Industry, Kasetsart University, 50 Phahon Yothin
Road, Bangkok, 10900, Thailand. Phone: 166-2-940–5634, Fax: bitter type) with the cyanide content , 50, 50 to 100 and
166-2-940-5634, e-mail: aapkrs@ku.ac.th. . 100 mg HCN equivalent per kilogram fresh weight,

 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.de

72 K. Piyachomkwan et al.
respectively [10]. Sweet cassava is preferably used for
direct consumption as staple food while the bitter type is
mostly processed to starch for industrial application.
During processing, a portion of cyanogenic compounds is
removed and some residues are still remaining in the fin-
ished products; the content is depending on processing
conditions. Various processes such as cooking, boiling,
drying, frying and fermentation are employed to suc-
cessfully detoxify cassava to a safe product used as food
or feed [1, 11–13].
The cyanogen content in cassava can be quantified by an
enzymatic method, of which the amount of total and indi-
vidual cyanogenic compound (including bound cyanide,
cyanohydrin and free cyanide) can be determined [14,
15]. For the total cyanogen content, the exogenous lina-
marase is added to an acid-alcohol extract of cassava, to
hydrolyze all bound cyanide to cyanohydrin, which is then
completely converted to free cyanide by pH adjustment
(to pH 6). The content of total free cyanide, representing
the total cyanogen content is then estimated from the
color intensity of an active chromogen and free cyanide
complex. When determined by only pH adjustment with-
out the addition of exogenous linamarase, the amount of
non-glucosidic cyanogen (i.e. cyanohydrin and free cya-
nide) can be evaluated. The difference between the total
cyanogen and non-glucosidic cyanogen content gives
the estimate of bound cyanide. Moreover, the amount of
cyanohydrin can be predicted from the difference be-
tween the content of non-glucosidic cyanogen and exist-
ing free cyanide, quantified without enzyme addition and
pH adjustment (at pH 4).
Cassava starch is one of the most important commercial
starches after corn, wheat and potato. The global cas-
sava starch industry ranges from small-scale to large-
scale factories. The small-scale process consists of wet-
milling of washed roots, washing the starch from milled
pulp on vibrating trays or in mixing tanks, sedimenting
the starch on a starch table or in starch ponds, and sun-
drying the products. Most cassava starch factories have
now developed from small- to large-scale with more
mechanized technology and shorter processing time. In
this starch process, washed roots are initially chopped
into small pieces and then fed to the rasper. Fresh
rasped-root slurry from the rasper is further pumped
through a series of extractors, from coarse to fine, to
produce starch slurry. The starch slurry from the fine
extraction is then concentrated by separators and water
is further removed by a dewatering centrifuge to produce
a moist starch cake for flash drying [16]. During this
starch process, cassava roots are subjected to a series
of different processing conditions, which may cause the
transformation of cyanogenic compounds and their
content. The individual quantification of these three cya-
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Stärke 57 (2005) 71–78
nogenic compounds is a prerequisite for developing the
effective means of cyanogen removal during the cassava
starch process and for monitoring the capability of pro-
ducing safe products. Therefore, this study demon-
strated the cyanogen balance and distribution of each
cyanogenic compound in cassava starch manufacturing
process.
2 Materials and Methods
In this study, the evaluation of mass and cyanogen bal-
ance of the cassava starch process of seven production
runs was conducted in a factory with a production ca-
pacity of around 100 t starch per day. The total mass of
raw materials, intermediates, products and wastes during
each run was recorded and the mass balance of starch
process was estimated according to Sriroth et al. [17].
The samples taken during the starch process including
fresh roots, washed roots, rasped roots, starch slurry from
coarse and fine extractors, starch slurry from separators,
starch cake, dried starch, liquid recycle, wastewater,
cassava pulp and peel of each run were collected for de-
termining the cyanogen content.
2.1 Analysis of cyanogen content
The contents of total cyanogen, non-glucosidic cyanogen
and free cyanide of processing samples were evaluated
using an enzymatic method according to O’Brien et al.
[15]. For the total cyanogen content (C1), the sample
extract in 25% ethanol/0.1 M phosphoric acid was incu-
bated with the enzyme linamarase (BDH Laboratory
Supplies, Poole, UK) at 30oC for 15 min. After incubation,
the pH of the enzyme-treated sample was adjusted to 6
with 0.2 M NaOH and 0.1 M phosphate buffer. Subse-
quently, the sample was assayed colorimetrically with
Chloramine T and pyridine/pyrazolone reagent at 620 nm,
using KCN as a standard. The total cyanogen content
was reported as mg HCN equivalent per kilogram sample
on dry weight basis. For the estimation of non-glucosidic
cyanogen (C2), the sample extract without enzyme treat-
ment was subjected to pH adjustment using 0.2 M NaOH
and 0.1 M phosphate buffer (pH 6) and the aliquot was
assayed colorimetrically as previously described. The
free cyanide of the extract (C3) was analyzed directly in
the same manner except that no enzyme treatment and
no pH adjustment were applied. Based on the contents of
total cyanogen, non-glucosidic cyanogen and free cya-
nide, the content of each cyanogenic compound was
then estimated as follows: Content of bound cya-
nide = Total cyanogens (C1)–non-glucosidic cyanogen
(C2) Content of cyanohydrin = Non-glucosidic cyanogen
(C2)–free cyanide (C3)
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Starch/Stärke 57 (2005) 71–78 Balance of Cyanogenic Compounds in Cassava Starch Process 73

2.2 Analysis of starch properties: 3 Results and Discussion

The contents of moisture, ash, sulfur dioxide and starch of
cassava starch products were analyzed according to the
AOAC methods [18, 19]. The microbial content was ana-
lyzed as the total plate count [20]. The pH of starch was
measured by a pH meter [21] and starch whiteness was
evaluated by a Whiteness meter (Kett, Tokyo, Japan). The
paste properties of cassava starch (3 g of starch with 14%
moisture content suspended in 25 g distilled water) were
determined by a Rapid Visco Analyser (RVA4, Newport
Scientific Pty, Ltd., Warriewood, Australia) [7].
In most modern cassava starch factories, the cassava
starch process begins with washing of harvested roots,
rasping of washed roots by the rasper, extracting by a
series of coarse and fine extractors, concentrating the
slurry by separators, dewatering the slurry by a centrifuge
and drying the starch cake by a flash dryer. The mass
balance of cassava starch production of a medium-scale
starch factory, i.e. 100 t starch per day is summarized in
Fig. 2. At this production capacity, around 400 t fresh
roots were consumed; the conversion ratio of root and

Fig. 2. Material balance in cassava starch manufacturing process. The values in parentheses repre-
sent the average 6 S.D., in unit of t/ day, of seven production runs.

 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.de

74 K. Piyachomkwan et al. Starch/Stärke 57 (2005) 71–78

starch was therefore around 4: 1, which was improved
(from 5: 1), presumably due to a variety improvement of
cassava with a higher starch content (25 to 30% wet
basis). The water consumption of starch production was
estimated to be 11.4 t per ton starch, which was usually
applied in most cassava starch factories. Although, water
consumption of cassava starch production is varied,
ranging from 10 to 30 t per ton starch [13], in practice, it is
always kept minimal (while the starch quality is main-
tained) to lower the production cost, i.e. cost of process
water and wastewater treatment. At this normal dosage of
water consumption, the discharged wastewater was
around 1,310685 t, accounting for 13 t wastewater per
ton starch. To optimize water consumption, water was,
therefore, generally recycled within the process before
being discharged. The cassava starch process generates
not only liquid waste, but also solid wastes including
cassava pulp and peel. The quantity of discharged pulp
(72.5% moisture content) was about 23% of the total root
weight being crushed.
By this improved technology, the cassava starch pro-
duced possessed a high quality, being premium grade
according to the Thai Standard for Tapioca Products [21].
The starch was very pure with a very low amount of
impurities (starch content . 89%, wet basis; Tab. 1). As a
premium-quality grade, produced cassava starch had a
moisture content less than 13% and ash content less than
0.15% (dry basis) (Tab. 1). The pH of starch was about 5.2
to 6.3, which was in the specified range of the Thai
standard. As a result of sulfur water application in the
process, some residual sulfur dioxide was present in the
finished products (approximately 110 ppm, dry basis;
Tab. 1). The sulfur dioxide content in cassava starch
ranged from 0, in case of no sulfur water application, to
100 ppm, depending on the purposes of application. With
the use of sulfur dioxide, the produced starch was very
white (whiteness . 95 Kett scale; Tab. 1). Cassava starch
is a root-reserved starch, which is usually easy to gelati-
nize. The pasting temperature of produced starch was
around 70.87C. In addition, when the starch is gelatinized,
cooked cassava starch provides a high viscous paste, but
does not markedly resist to shearing, therefore posses-
sing a high breakdown value. The paste properties of
cassava starch collected in this study are summarized in
Tab. 1. It is interesting to note that the properties of col-
lected starches were consistent, suggesting effective
quality control in the cassava starch process.

Tab. 1. Chemical, microbiological and pasting properties of cassava starch samples collected from starch process of 7
production runs.

Properties Production runs

1 2 3 4 5 6 7 Average

Chemical properties*
Starch content
[%, wet basis] 89.49 6 0.10 89.84 6 0.10 89.45 6 0.45 90.06 6 0.07 89.45 6 0.45 89.39 6 0.09 88.80 6 0.06 89.4960.19
Moisture content [%] 11.40 6 0.14 11.71 6 0.01 12.11 6 0.04 11.10 6 0.03 12.28 6 0.14 11.37 6 0.07 12.44 6 0.06 11.7760.07
Ash content 0.14 6 0.00 0.15 6 0.01 0.15 6 0.00 0.13 6 0.00 0.15 6 0.01 0.15 6 0.00 0.14 6 0.01 0.1460.00
[%, dry basis]
Sulfur dioxide [ppm,
dry basis] 129 6 1 118 6 0 125 6 1 100 6 0 107 6 0 106 6 0 93 6 0 111 6 1
pH 5.23 6 0.04 5.29 6 0.00 5.33 6 0.06 5.74 6 0.01 6.28 6 0.00 5.57 6 0.01 5.99 6 0.04 5.6360.02
Whiteness 96.1 6 0.1 95.7 6 0.1 95.8 6 0.1 94.4 6 0.1 95.3 6 0.1 95.1 6 0.1 95.3 6 0.0 95.3 6 0.1
Microbiological pro-
perties
Total Plate Count
[CFU/g] 8.33 6 102 4.00 6 102 3.73 6 102 1.08 6 104 8.70 6 103 1.76 6 103 1.94 6 103 3.54 6 103
Pasting properties*
Pasting tempera-
ture [7C] 71.4 6 0.1 73.5 6 0.1 69.6 6 0.2 71.2 6 0.2 70.8 6 0.3 69.4 6 0.0 69.6 6 0.8 70.8 6 0.3
Peak viscosity [RVU] 340 6 1 347 6 3 341 6 2 343 6 2 353 6 4 354 6 6 353 6 2 347 6 3
Trough [RVU] 122 6 4 140 6 2 126 6 0 118 6 1 128 6 2 140 6 2 136 6 2 130 6 2
Breakdown [RVU] 218 6 3 207 6 1 215 6 2 225 6 1 224 6 3 214 6 3 217 6 0 217 6 2
Final viscosity [RVU] 182 6 1 200 6 5 187 6 3 198 6 1 203 6 7 227 6 4 212 6 4 201 6 4
Setback [RVU] 60 6 6 60 6 3 61 6 3 80 6 0 75 6 5 87 6 2 76 6 2 71 6 3

* Value are the average 6 S.D. of two determinations.

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Starch/Stärke 57 (2005) 71–78 Balance of Cyanogenic Compounds in Cassava Starch Process 75

Tab. 2. Mass balance and cyanogen balance of cassava starch process*.

Sample / process Production

1 2 3 4 5 6 7 Average

Fresh roots
Quantity [t/day] 360 432 471 455 426 410 399 422 6 37
Cyanide content [mg HCN kg21, dry weight] 237.5 255.9 260.6 302.8 272.7 317.1 339.4 283.7 6 36.8
Cyanide content [kg/day] 27.63 32.66 35.99 43.21 35.97 43.67 43.79 37.59 6 6.30
% Cyanide (to total amount in fresh roots) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 6 0.0
Rasped roots
Quantity (t/day) 919 964 1,040 866 903 911 920 932 6 56
Cyanide content [mg HCN.kg21, wet basis] 46.0 48.8 47.2 68.5 53.8 68.1 63.9 56.6 6 10.0
Cyanide content [kg/day] 42.25 46.99 49.09 59.34 48.59 62.01 58.74 52.43 6 7.51
% Cyanide (to total amount in fresh roots) 152.9 143.9 136.4 137.3 135.1 140.3 134.1 140.0
Slurry from extractor
Quantity (t/day] 771 822 902 830 861 850 878 845 6 43
Cyanide content [mg HCN.kg21, wet basis] 33.5 35.4 37.3 47.3 37.4 47.8 46.8 40.8 6 6.2
Cyanide content [kg/day] 25.85 29.12 33.68 39.28 32.17 40.61 41.04 34.54 6 5.96
% Cyanide (to total amount in fresh roots) 93.6 89.2 93.6 90.9 89.4 92.6 93.7 91.8 6 2.0
Slurry from separator
Quantity (ton/day) 313 346 424 416 427 417 353 385 6 46
Cyanide content (mg HCN.kg21, wet basis) 11.4 10.0 12.0 13.8 10.1 11.9 10.7 11.4 6 1.4
Cyanide content (kg/day) 3.56 3.44 5.09 5.76 4.30 4.98 3.77 4.41 6 0.88
% Cyanide (to total amount in fresh roots) 12.9 10.5 14.1 13.3 12.0 11.3 8.6 11.8 6 1.9
Starch cake from dewatering centrifuge
Quantity [t/day] 131 136 149 149 147 141 136 141 6 7
Cyanide content [mg HCN.kg21, dry basis] 7.8 7.5 7.4 8.3 8.3 7.0 7.1 7.6 6 0.5
Cyanide content [kg/day] 0.66 0.68 0.75 0.84 0.82 0.64 0.65 0.72 6 0.08
% Cyanide (to total amount in fresh roots) 2.4 2.1 2.1 1.9 2.3 1.5 1.5 2.0 6 0.4
Dried starch
Quantity [t / day] 96 102 115 113 112 103 104 106 6 7
Cyanide content [mg HCN.kg21, dry basis] 1.9 1.7 1.0 1.8 0.0 1.6 1.3 1.3 6 0.6
Cyanide content [kg/day] 0.16 0.16 0.10 0.18 0.00 0.14 0.12 0.12 6 0.06
% Cyanide (to total amount in fresh roots) 0.6 0.5 0.3 0.4 0.0 0.3 0.3 0.3 6 0.2
Wastewater
Quantity [t/day] 1,392 1,419 1,416 1,556 1,348 1,307 1,283 1,389 6 90
Cyanide content [mg HCN kg21, wet basis] 18.4 20.5 23.7 26.0 25.0 30.0 31.5 25.0 6 4.7
Cyanide content [kg/day] 25.68 29.09 33.57 40.45 33.71 39.14 40.42 34.58 6 5.78
% Cyanide (to total amount in fresh roots) 93.0 89.1 93.3 93.6 93.7 89.2 92.3 92.0 6 2.0
Cassava pulp
Quantity [t/day] 90 90 98 104 76 126 104 98 6 16
Cyanide content [mg HCN kg21, dry basis] 56.4 59.6 60.6 60.2 61.1 91.4 94.7 69.2 6 16.4
Cyanide content [kg/day] 1.27 1.57 1.67 1.91 1.43 3.40 2.71 2.00 6 0.78
% Cyanide (to total amount in fresh roots) 4.6 4.8 4.6 4.4 4.0 7.8 6.2 5.2 6 1.3
Water vapor (from flash dryer)**
Quantity [t/day] 35 33 34 36 35 38 32 35 6 2
Cyanide content [kg/day] 0.50 0.53 0.64 0.66 0.62 0.50 0.53 0.57 6 0.07
% Cyanide (to total amount in fresh roots) 1.8 1.6 1.8 1.5 1.8 1.1 1.2 1.6 6 0.3

* Data were collected from 7 production runs.

** Data were calculated from the mass and cyanogen balance.

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76 K. Piyachomkwan et al. Starch/Stärke 57 (2005) 71–78

Tab. 3. Distribution of total cyanogenic compounds during starch processing*.

Sample/process Content of total cyanogenic compounds [kg HCN equivalent/day] %Cyanide

distribution**
1 2 3 4 5 6 7 Average

Fresh roots 27.63 32.66 35.99 43.21 35.97 44.19 43.79 37.63 100.00
Washed roots 27.13 30.69 35.34 41.18 33.59 44.02 43.75 36.53 96.93
Rasped roots 42.25 46.99 49.09 59.34 48.59 62.01 58.74 52.43 140.01
Starch slurry from coarse extractor 1 33.84 39.35 40.57 50.16 41.22 50.44 49.30 43.55 116.15
Starch slurry from fine extractor 1 28.06 34.07 36.37 41.72 35.00 42.02 43.19 37.20 99.21
Starch slurry from fine extractor 2 25.86 29.12 33.68 39.28 32.17 40.61 41.04 34.54 91.75
Starch slurry from separator 1 6.43 8.33 9.68 19.66 11.45 13.27 15.03 11.98 31.04
Starch slurry from separator 2 3.56 3.44 5.09 5.76 4.30 4.98 3.77 4.41 11.82
Starch cake from dewatering 0.66 0.68 0.75 0.84 0.82 0.64 0.65 0.72 1.96
centrifuge
Dried starch 0.16 0.16 0.10 0.18 0.20 0.14 0.12 0.15 0.41
Liquid recycle to rasper 15.13 16.30 13.75 18.16 15.00 17.99 14.98 15.90 43.08
Liquid recycle from dewatering 2.90 2.76 4.34 4.92 3.48 4.34 3.12 3.69 9.86
centrifuge
Wastewater 25.68 29.09 33.57 40.45 33.71 39.14 40.42 34.58 91.93
Cassava pulp 1.27 1.57 1.67 1.92 1.43 3.41 2.71 2.00 5.19
Water vapor (from flash dryer) 0.50 0.53 0.64 0.66 0.62 0.50 0.53 0.57 1.5
Peel 0.001 0.008 0.005 0.004 0.004 0.011 0.01 0.006 0.02

* Data were collected from 7 production runs.

Amount of total cyanogen of evaluated samples
** % Cyanide distribution = 6 100
Amount of total cyanogen in fresh roots

Tab. 4. Ratio of bound cyanide, cyanohydrin and free cyanide of samples collected during starch processing*.

Sample/process Ratio of bound cyanide : cyanohydrin : free cyanide

1 2 3 4 5 6 7 Average

Fresh roots 67 : 31 : 2 64 : 33 : 3 64 : 31 : 5 61 : 36 : 3 65 : 32 : 3 63 : 34 : 3 61 : 37 : 2 64 : 34 : 3
Washed roots 66 : 17 : 7 63 : 33 : 4 62 : 30 : 8 60 : 36 : 4 65 : 31 : 4 62 : 35 : 3 62 : 31 : 7 63 : 32 : 5
Rasped roots 17 : 65 : 18 32 : 57 : 11 21 : 60 : 19 22 : 62 : 16 28 : 60 : 12 20 : 68 : 12 14 : 63 : 23 22 : 62 : 21
Starch slurry from coarse 18 : 64 : 18 31 : 58 : 12 20 : 60 : 20 18 : 58 : 24 18 : 58 : 24 27 : 64 : 9 9 : 75 : 16 20 : 62 : 18
extractor 1
Starch slurry from fine 11 : 68 : 21 21 : 63 : 16 15 : 53 : 32 20 : 58 : 22 13 : 65 : 22 28 : 63 : 9 10 : 77 : 13 17 : 64 : 19
extractor 1
Starch slurry from fine 11 : 66 : 23 15 : 65 : 20 15 : 49 : 37 20 : 55 : 25 20 : 61 : 19 31 : 61 : 8 9 : 78 : 13 17 : 62 : 21
extractor 2
Starch slurry from separator 1 6 : 81 : 13 16 : 65 : 19 16 : 53 : 31 20 : 65 : 15 19 : 62 : 19 25 : 70 : 5 8 : 78 : 14 16 : 68 : 16
Starch slurry from separator 2 12 : 67 : 21 13 : 62 : 25 20 : 50 : 31 19 : 75 : 6 19 : 65 : 16 18 : 78 : 4 8 : 77 : 15 15 : 68 : 17
Starch cake 8 : 70 : 22 12 : 61 : 27 7 : 72 : 21 15 : 74 : 11 19 : 64 : 17 14 : 80 : 6 7 : 81 : 12 12 : 72 : 16
Dried starch 10 : 73 : 17 11 : 71 : 18 12 : 58 : 30 7 : 84 : 9 21 : 64 : 15 10 : 86 : 4 7 : 81 : 12 11 : 74 : 15
Liquid recycle to rasper 14 : 69 : 17 24 : 55 : 21 31 : 54 : 15 32 : 37 : 31 39 : 51 : 10 42 : 51 : 7 32 : 46 : 22 30 : 52 : 18
Liquid recycle from dewatering 8 : 62 : 30 11 : 60 : 29 20 : 60 : 20 13 : 57 : 30 9 : 66 : 25 36 : 52 : 12 18 : 67 : 15 17 : 60 : 23
Wastewater 12 : 69 : 19 12 : 72 : 16 15 : 57 : 28 26 : 54 : 20 15 : 66 : 19 16 : 72 : 12 5 : 66 : 29 15 : 65 : 20
Cassava pulp 8 : 59 : 33 14 : 60 : 26 19 : 52 : 29 12 : 58 : 40 21 : 53 : 26 7 : 65 : 28 23 : 48 : 19 15 : 55 : 30
Peel 59 : 29 : 12 55 : 38 : 7 60 : 34 : 6 69 : 26 : 5 61 : 35 : 4 65 : 29 : 6 66 : 31 : 3 63 : 31 : 6

* Data were collected from 7 production runs.

The cyanogen balance of the cassava starch process was the roots (the total cyanide content 240 to 340 mg HCN
also determined for seven production runs (Tab. 2). The equivalent per kilogram, dry weight) of which their cya-
sole source of cyanogen in the starch process was from nide content could be varied as influenced by the genetic

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Starch/Stärke 57 (2005) 71–78 Balance of Cyanogenic Compounds in Cassava Starch Process
and environment factors. Under these premises (i.e. an
average daily root consumption of 420 t and an average
cyanide content in fresh roots of 283 mg HCN equivalent
per kilogram), approximately 37 kg HCN equivalents were
introduced each day in the starch process. In starch pro-
duction, the roots were initially washed by recycled water
obtained from the separators. Washing slightly removed
cyanide residues from roots due to the water-solubility of
the glucosides (4%, Tab. 3). Washed roots were then
transferred to a rasper in which liquid recycled from the
extractor was used. Some portions of cyanogen in liquid
recycle were then accumulated, resulting in a greater
concentration of cyanogen compounds at this processing
stage. The cyanide content of starch slurry was then
reduced during extraction and separation (Tab. 3). After
dewatering, only 2% of cyanogen residues were left in the
starch cake and further removed by drying with hot air. As
a result, less than 0.4% of the total cyanogen originally
present in the raw materials was left in the finished prod-
ucts (the total cyanide content in dried starch was around
0 to 2 mg HCN equivalent per kilogram, dry weight). Most
cyanogenic compounds appeared in liquid (92%) and
solid waste, i.e. cassava pulp and peel (5.2%). A small
amount of cyanogen was lost with the water vapor (1.5%)
during starch drying. In the starch process, liquid was
recycled to minimize the amount of wastewater. There
were usually three types of liquid recycle, one from the
dewatering centrifuge to separators, one from separators
to root washers and one from the coarse extractors to the
rasper. The liquid recycle from separators to root washers
was, in general, discharged as wastewater with a high
cyanide content (92% of total cyanogen in roots) and did
not greatly impact the cyanide content in products. How-
ever, liquid recycle from dewatering centrifuge to separa-
tors and the coarse extractor to the rasper could cause
the accumulation of cyanogen in the process; the effect of
the latter was extreme (% cyanogen distribution = 43% of
total cyanogen in roots). With respect to this knowledge, it
is likely to produce low-cyanide starch by adjusting water
circulation. For instance, a proportion of the liquid recycle
to the rasper, after passing through the decanter equip-
ped in the process line to collect starch loss, should be
discharged to minimize the cyanogen circulating in the
process. The extent of liquid recycle being discharged
should be a compromise between required starch quality
and production cost.
In addition, the ratio of each cyanogenic compound
including bound cyanide, cyanohydrin and free cyanide
was evaluated. The results demonstrated the transfor-
mation of cyanogenic compounds during starch proces-
sing (Tab. 4). Bound cyanide as b-glucoside was pre-
dominantly found in fresh roots (64% of total cyanide in
roots). Theoretically, fresh roots with undamaged tissues
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
77
should contain a high amount of bound cyanide and a
negligible amount of cyanohydrin and free cyanide. How-
ever, fresh roots in the factory exhibited some cyanohy-
drin and a certain amount of free cyanide (34 and 3% of
total cyanide in roots, respectively). This presumably
might be due to the harvest protocol, which introduced
tissue damage, and the post-harvest handling (time,
temperature, etc.) of the raw materials prior to proces-
sing, allowing endogenous enzymes to hydrolyze bound
cyanide to cyanohydrin and free cyanide [22]. This effect
was more pronounced in samples obtained from the ras-
per, because bound cyanide remarkably decreased from
63 to 22% and the cyanohydrin as well as free cyanide
content increased from 32 to 62% and from 5 to 21%,
respectively. The ratios of each cyanogenic compound in
samples collected after rasping were similar, because
cyanohydrin compounds were primarily present. Accord-
ingly, it is possible to lower the cyanide content in starch
products by removing cyanohydrin compounds by pH
adjustment close to neutral pH.
4 Conclusion
The study of the cyanogen balance and the distribution of
cyanogenic compounds including bound cyanide, cya-
nohydrin and free cyanide throughout the starch process
provides very useful information resulting in potential
modifications of starch processing to enable efficient
production of low-cyanide cassava starch.
Acknowledgement
This work was kindly supported by the National Center for
Genetic Engineering and Biotechnology, National Sci-
ence and Technology Development Agency, Ministry of
Science and Technology, Thailand. The author is also
grateful to Khow Chang Eah Tapioca and Sago Industry
Co., Ltd. for their kind cooperation in this work.
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(Received: July 28, 2004)
(Accepted: September 29, 2004)
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