Proceedings of the 19th IAHR-APD Congress 2014, Hanoi, Vietnam

ISBN xxx-xxxx-xx-x

RESEARCH ON APPLICATION OF SHRIMP SHELL WASTES IN TREATMENT OF WHITE

EFFLUENT FROM PAPER AND PUPL PRODUCTION INDUSTRIES

Assoc. Prof, Dr VU HOANG HOA(1), M.Sc. TRAN MINH DUNG(2), VU THANH TRA(3), PHAN THI HOAI CAM(4), DO VAN TIEN(5)

(1)
Water Resources University, Hanoi, Vietnam, email: hoanghoavu@yahoo.com
(2)
Water Resources University, Hanoi, Vietnam, email: dungmt@wru.vn
(3)
Water Resources University, Hanoi, Vietnam, email: travt07@wru.vn
(4)
Water Resources University, Hanoi, Vietnam, email: campth07@wru.vn
(5)
Water Resources University, Hanoi, Vietnam, email: tiendv07@wru.vn

ABSTRACT
Chitosan is a useful product from shrimp shell wastes. It has significant role in many areas such as medicine,
agriculture, industry, biotechnology... To develop application of Chitosan in wastewater treatment, research has been
conducted on the biological flocculation ability of Chitosan to treat white effluent from paper industry to recover pulp
lost. First, Chitosan was extracted from shrimp shell and then Jar test model was built to find optimal conditions for
flocculation in the treatment process. The experimental results showed that Chitosan optimal dosage is 100 mg for
treatment of each litre of the paper white effluent at normal temperature, resulting in total suspended solid (TSS)
reduced by 95.43% and true colour units reduces by 91.60%. Thus, application of Chitosan derived from seafood
processing industry waste will contribute to improving the economic resources, reducing solid waste generation and
wastewater pollution, helping protect the environment.

Keywords: Chitin; Chitosan; shrimp shells; white effluent; flocculation; Jar test.

1. INTRODUCTION produced products from these materials. Chitin has been

used in paper production process due to its good
Fisheries are a key sector in the national economy.
adhesion on the surface, creating membrane materials
According to the latest statistics in 2012 from the Seafood
which can prevent dehydration and have antifungal and
Research Institute, Vietnam now has about 1,015 seafood
antibacterial capability; when used as ingredient can
processing facilities with large and small scale, and
create paper products with smooth surface with high
exports over 140,000 tons of fisheries products per year.
permeability. Chitin is also applied in the food processing
However, the fisheries industry generates a large amount
industry and cosmetics production. Currently there have
of waste - around 70,000 tonnes/ year (Vietnam Cleaner
been some studies on extraction of Chitosan from
Production Center, 2009). Particularly in processing of
shrimp, crab and gave some conclusions on possible
frozen seafood, each tonne of shrimp product will
application of Chitosan in treatment of wastewater from
discharge 0.75 tons of waste to the environment, most of
various industries (Kumar, 2000; Kim, et al., 1997; No, et
which is shrimp shells and tails. Only a minor amount of
al., 2000, Knorr, 1983). However, the application of
shrimp shells and tails waste is dried or sundried, or
Chitosan in the fields of agriculture, medicine, industry,
finely ground for use as animal feed. Most of the unused
and particularly in wastewater treatment is still new and
shrimp waste undergoes microbial decomposition in
not yet developed in Vietnam.
aerobic conditions, generating foul smelling substances
such as CH 4, H2S, NH 3, ... polluting the environment, On the other hand, the issue of water resources
affecting health of local communities. management and wastewater treatment in Vietnam has
become pressing, especially in manufacturing of pulp
Many studies have demonstrated that shells of
and paper. This industry uses large amount of water,
crustaceans, especially shrimp shell contains about 21 %
discharging wastewater at the average 300 m 3/ ton of
-24 % of Chitin [C8H13O5N]n - a polysaccharide that itself
paper product, especially at paper formation stage
and its Chitosan derivatives [C6H11O4N] have many
(Vietnam Cleaner Production Center, 2009). Effluent from
useful features such as antibacterial, antifungal , antiviral,
this stage contain lots of pulp, fillers, pigments and
anti -inflammatory, high biological harmony properties,
additives which is refered to as white effluent, which, if
capable of self-biodegradable, flexible and
not treated, will cause a negative impact to human,
environmentally friendly material (Kim and Rajapakse,
animal and aquatic resources in waters receiving the
2005; Qin et al., 2006; Sandford, 1989). With these
effluent. Therefore, research on application of Chitosan as
capabilities, many countries have conducted research and
biological coagulant in wastewater treatment for the
1
paper industry will reduce generation of hamrful paper
substances into the environment, help recover pult
resources and handle large amount of waste from
seafood processing industry.
This paper presents some results of research on biological
flocculation ability of Chitosan derived from shrimp shell
waste to reduce turbidity, color, suspended solids in
paper industry effluent. The results would open up a
future for the application of Chitosan in wastewater
treatment not only in the paper industry, but also for
many other industries.
2. RESEARCH METHODS
In the composition of shrimp shell, Chitin volume
accounts for approximately 24%, the remainder consists
of protein, minerals and color substance which need to be
removed to extract Chitin (Thiet Nguyen Van, Do Ngoc
Tu, 2007). The research applies Jar test experimental
model for empirical studies of wastewater treatment at
Anh Duc Tissue Plant (in Vinh Phuc, Vietnam) to explore
biological flocculation ability and provide conclusions
about the effectiveness of the paper wastewater treatment
through finding the optimal concentration of Chitosan in
the laboratory.
Immerse the Chitin at approximately 75% acetylatation in
40% NaOH solution for 48 hrs at room temperature to
obtain Chitosan product with bright white colour.
2.3 Experiment to find the optimal Chitosan dose
The purpose of the experiment is to find the optimal
conditions for Chitosan product during flocculation of
wastewater treatment process of paper production.
Use consecutively different doses of 1% Chitosan
solution, corresponding to 50 mg, 75mg, 100mg, 125mg,
150mg, 200mg, 225mg, 250mg, 275mg, 300mg and 400mg
Chitosan for a glass containing 1 liter of effluent of paper
production.
2.4 Compare efficiency of white effluent treatment by
Chitosan, alum and PAC around the optimum point
Perform experiments using dual alum KAl(SO 4)2.12H 2O
and Poly Aluminium Chloride [Al 2(OH) nCl6.n.H 2O]m
(PAC) for treatment of TSS and color in white effluent of
paper production to compare the efficiency of the
treatment by Chitosan. The results are then reviewed to
make a general comment about the pros and cons of
Chitosan compared with traditional treatment methods.

Chitosan when enters paper white effluent shows clear Determine the optimal amount of alum
property of a colloidal particle. The interactions between (KAl(SO 4)2.12H 2O): experiment with varying alum
the colloidal particles are possible due to instability of amount of 750mg, 875mg, 1000mg, 1062mg, 1125mg, and
their original state and rapid mixing mechanism to 1,250mg.
facilitate exposure among them for electronic Determine the optimal amount of PAC: experiment with
neutralization, which accelerates the process of creation varying amount of PAC of 125mg, 250mg, 375mg, 500mg
of floculation clusters which can easily settle down. The and 562mg.
suspension components in the white effuent such as fine
cellulose fibre, pulp particles, additives... following arrest 3. RESEARCH RESULTS
mechanism will be settled down along with large flocs
and the visible color of wastewater thereby reduces. The 3.1 Results of Chitin experiment
optimal Chitosan concentration is determined to be the
concentration in laboratory test which helps remove color From shrimp shell waste which was cleaned in pre-
and TSS to the lowest levels. The effect of Chitosan in processing, conduct experiment of Chitin extraction
wastewater treatment are also assessed through according to the steps described above to obtain Chitin in
comparative experiments with common flocculants such the form of pale pink flakes. Chitin extraction efficiency
as alum and PAC on their ability of forming flocs and is from 33% to nearly 34%.
reduction of color and turbidity in post treatment of The efficiency of extraction process is calculated using the
wastewater. below formula:

2.1 Extraction of Chitin m2

E (%) = 100%
m1 [1]
First, crude shrimp shells are collected, washed and
preliminarily processed to removes impurities; then
dried at temperature of 400C. Step 1 demineralization where, m1: initial volume of shrimp shells (g)
of shrimp shell: dried shrimp shells are soaked with m2: amount of Chitin obtained (g)
10% HCl solution for 12 hours at room temperature (23- E : efficiency of the process (%)
250C). Then the shells are washed to neutral state by
purified water. Step 2 removal of protein: shrimp Table 1. Results of Chitin production from shrimp shells
shells after demineralization are soaked in 3% NaOH Shrimp shells Volume after Efficiency of
solution (pH = 12). Heat the mixture at a temperature of Time
(g) extraction (g) extraction (%)
90 - 950C for 5.5 hours to hydrolyze protein. Step 3
1 7.38 2.50 33.87
color removal: soak the shells in solution of 1% H2O2
2 8.05 2.72 33.79
for 12 hours at room temperature. The shells are dried at 3 8.05 2.69 33.42
temperature of 600C to obtaine Chitin product with 4 8.05 2.68 33.29
pinkish color.
3.2 Experimental results of Chitosan production
2.2 Treatment of Chitosan

2
Extraction efficiency of Chitosan product, according to 460
chemical method, ranged from 60-62%. Chitosan product
400
is obtained in the form of white flakes. The TSS level before treatment

The TSS level (mg/l)

21
Chitosan is a polymer insoluble in water, alkaline 300
The TSS level after treatment

solutions and organic solvents because of its stable and

215
rigid crystal structure. But Chitosan has the ability to 200
203

dissolve in a number of inorganic and organic acids at 158 177 183 192
130
certain pH values after mixing, thus Chitosan 1% solution 100
105
is produced using 1% acetic acid solution. The process 59
obtains Chitosan solution in viscosity form, with almost 21 45
0
transparent color. 50 75 100 125 150 200 225 250 300 350 400

The Chitosan level (mg)

3.3 Experimental results to find the optimal Chitosan
dose Figure 1. TSS reduction after treatment with Chitosan 1%

The process of sedimentation occurs when particles settle 1490

down to bottom due to the density of the particles is
higher than that of surrounding liquid environment. The 1200

The coloring level (Pt-Co)

ability of sediment deposition is closely related to the 125
Coloring before treatment

kinematic viscosity of the liquid n (m 2.s-1), with n as a Coloring after treatment

1000
function of temperature. As the temperature increases, 980
915
the viscosity decreases; on the other hand when the 830
800
viscosity of the liquid increases, the deposition velocity 609 744
560 520
will decrease. 413
400
According to Einstein the viscosity of colloidal systems 335
125
228
depends on the volume and shape of colloidal particles: 0
50 75 100 125 150 200 225 250 300 350 400
h = h0 ( 1 + a w ) [2] The Chitosan level (mg)

The higher concentration of particles the greater the
viscosity of the system, therefore the viscosity of the
colloidal system increases according to reduction of the
particle size. Chitosan is a high molecular compound
with hydrodynamic properties of flexible and elastic
molecules therefore it has high viscosity because of the
presence of conjugated molecules in the solution. Too
high viscosity of solution is undesirable during
coagulation process because it reduces the possibility of
flocculation and sedimentation of suspended solids.
Chitosan is the agent that binds the flocks containing
cellulose pulp in white effluent to form larger flocks
which easier to settle down. A 1% Chitosan solution with
good solubility in acetic acid will form complete
colloidal, which helps increase affinity of suspended
colloidal particles or small sediment particlesl.
The decisive factor for flocculation efficiency is Chitosan
doses. Basically, insufficient or excess dosage will lead to
decreased efficiency. The effect of colloidal flocculation
also depends on the mixing conditions, the intensity of
stirring and the stirring time: the quicker, the smoothier
mixing and the higher temperature of the solution the
higher flocculation efficiency. Alkaline level is also very
important to facilitate the sticking together of dirt
elements. In addition, pH factor not only affects the
surface of coagulants but also affects the stability of the
system. In addition, the solubility of Chitosan in water
solution is also affected by pH value. In this research the
experiments were performed with pH=6.5 of paper mill
effluent at Anh Duc Plant.
Figure 2. Coloring reduction after treatment with Chitosan 1%
The study results showed that for glasses of effluent,
when added Chitosan amount increases from 125 mg to
400 mg, the treatment efficiency of TSS and colour
reduces. Although the influencing factors such as mixing
speed, mixing time, pH conditions all ensure solubility of
Chitosan and flocculation process to happen completely,
the obtained treatment performance of TSS reduces from
90.20% to 53.26% and the color reduction performance
reduces from 84.70% to 34.23% compared to the original
effluent status.
Thus, increased amount of Chitosan leads to increased
viscosity of effluent. As the viscosity is proportional to
the dose used, the electronic charged particles of
wastewater and flocculants are more difficult to contact
each other, resulting in reduced flocculation. As the
Chitosan residue sticks together, the colloidal system
become more durable, making the water turbid, less
flocculation or creating unwanted side products. Less
amount of settled flock means more amount of total
suspended solids (TSS) in the wastewater exist. Turbidity
which depends on suspended components in the effluent
also increases and hence the color treatment efficiency
reduces.
Experiment with Chistosan amount of 50mg and 75mg
for glasses of effluent shows that this Chitosan
concentration is too low to treat the large amount of TSS
and color of the original effluent to efficient flocculation
of the suspended solids in wastewater. The treatment
performance of TSS is 77.17% - 87.17% and of colour is
62.4 % -77.52%, which is lower that desired rate.
The Chitosan dose for best treatment outcomes is 100mg/
per liter of effluent in room temperature conditions,
which gives TSS treatment rate of up to 95.43% and
3
coloring drops to 91.61 % compared with the initial state. 428
This is the optimal dose Chitosan for the paper The TSS level before treatment
wastewater at Anh Duc Plant. 6
The TSS level after treatment
60
54
3.4 Experimental results comparing treatment efficiency

The TSS level (mg/l)

between Chitosan with alum and PAC
When adding alum in wastewater, first it cause slight 40
39
increases ion capacity and alum at the same time
performs hydrolysis reaction with water to form metal
20
hydroxides flocks which have the ability to attract 20
suspended particles in the water falling under gravity 10
faster and settling down to the bottom. However, when 6

using aluminum salts to treat coloring in water, it is often 0

difficult to determine the optimal amount of flocculants 125 250 375 500 562

for treatment, therefore this can result to unnecessary The PAC level (mg)

excess of flocculants. Figure 5. TSS reduction after treatment with PAC

The process of coagulation occurs due to the hydrolysis

1530
reaction of alum is summarized as follows:
Coloring level before treatment
Al3+ + 3HOH Al(OH) 3 + 3H+ [3] 33
Coloring level after treatment

The coloring level (Pt-Co)

358 400
345
300
The TSS level before treatment
The TSS level (mg/l)

38
The TSS level after treatment 197
200 200

110
50
100 33
68 73 68
56 0
38 45 125 250 375 500 562
The PAC level(mg)
0
750 875 1000 1062 1125 1250 Figure 6. Coloring reduction rate after treatment with PAC
The alum level (mg)

Figure 3. TSS reduction after treatment with alum The optimal dose of PAC for highest efficiency of
wastewater treatment (TSS reduction: 98.6% and color
reduction: 97.84 %) is 250mg/litre of paper effluent,
1450
Coloring before treatment greater than 2.5 times the optimal Chitosan dose
110
Coloring after treatment (100mg/litre wastewater).
800
The coloring level (Pt-Co)

760

650
600

456
410
400
281

200
110

0
750 875 1000 1062 1125 1250
The alum level (mg)

Figure 4. Coloring reduction rate after treatment with Alum

The optimal alum dosage which gives highest efficiency
of wastewater treatment (TSS reduction 89.38% and color
reduction: 92.4%) is 1000mg/per litre of paper effluent,
greater than 10 times the optimal dose Chitosan (100mg/
per litre of wastewater) .
Figure 7. Compare the treatment effiency between alum, Chitosan
and PAC
General comments: Only a small amount Chitosan
(100mg/litre wastewater) will give the efficiency of
treatment equivalent to PAC flocculent. On the other
hand, alum gives lower treatment efficiency than
Chitosan, and with much more dose for treatment. For
wastewater treatment using Chitosan as flocculation is
the most suitable method.

4
4. CONCLUSION AND RECOMMENDATION Properties and Applications. Ed. by Skjk-Brk,
G., Anthonsen, T. and Sandford, P. Elsevier Applied
Derived Chitin has the form of pink flakes because of
Science, London, 51-69.
shrimp shells color residue. The efficiency of Chitin
Stevens, W. F. (2001). Production of chitin and chitosan:
preparation is from 33% to nearly 34% whereas shrimp
Refinement and sustainability of chemical and
shell only contains 21% - 24%. Thus, obtained Chitin
biolorical processing. Chitin and chitosan in life
from this is still impure. A possible reason might be due
science, Japan, 293.
to the used shrimp shells are not completely free from
Tokura, S. and Nishi, N. (1995). Specification and
impurities since the efficiency of Chitin retrieval depends
characterization of chitin and chitosan. In: Chitin and
on the amount of the protein in the sample. In addition,
Chitosan: The Versatile Environmentally Friendly
the extraction process can involve error because of
Modern Materials, 68-86.
external conditions such as temperature, wind, The
Thiet Nguyen Van, Do Ngoc Tu (2007).Researching
final obtained product should have the form of white
extraction of chitin from shrimp shells by biological
flakes.
methods. Journal of science and technology, 45 (3).
Through experiments, the efficiency of reducing TSS and Yo Li Chen (2008). University Sains Malaysia. Preparation
colour is highest at 100 mg Chitosan/litre of paper and characterization of Water soluble Chitosan gel for skin
production wastewater at room temperature conditions. hydration.
Comparing with alum and PAC solution, the ability of Information Center for Agriculture and Rural
flocculation of the paper wastewater using Chitosan is Development, (2013). Vietnam fishery industry in 2012
significantly higher. and outlook for 2013. Institute of Policy and Strategy for
Agriculture and Rural Development. Ministry of
It can be said production of Chitin and Chitosan from the Agriculture and Rural Development, Vietnam.
waste of fisheries processing industry is the right Vietnam Cleaner Production Center (2009). Document
direction to reduce generation of and pollution by solid guides the cleaner production in the pulp and paper
waste, increasing economic benefits for fisheries industry Institute for Environmental Science and
processing businesses. Further research is needed on Technology, Hanoi University of Science and
improving the efficiency of Chitin and Chitosan Technology.
production, and especially on the application of Chitosan Vietnam Environment Administration (2011). Technical
flocculation for wastewater treatment. Documentation guides assessing the suitabilility of
wastewater treatment technology and introducing some
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