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

ISBN xxx-xxxx-xx-x

POSSIBILITY OF RE-USING OYSTER SHELLS IN ACIDIC WASTEWATER TREATMENT

DUNG. TRAN MINH(1), NHAN. PHAM THI THANH(2), QUANG. HOANG HA(3) & HUYEN. PHAM THANH(4)
(1) Water Resources University, Hanoi, Vietnam, email: dungtm@wru.vn
(2) Water Resources University, Hanoi, Vietnam, email: nhanptt07@wru.vn
(3) Water Resources University, Hanoi, Vietnam, email: quanghh07@wru.vn
(4) Water Resources University, Hanoi, Vietnam, email: huyenpt07@wru.vn

ABSTRACT
With CaCO3 component made up to 95% (Davis T.A et al., 2000), oyster shells are similar in composition with limestone.
The objective of this research is to present the capability of oyster shells in treating acidic wastewater from Thanh Thuy
metal craft village. Based on jar test experiments to find the optimum conditions for the process including: dimension of
shells, calcination time, calcination temperature, volume of shells and exposure time. The experimental results were
demonstrated that: shells sized from 2 to 5 centimeters; calcinated in 6000C in 1 hour, brought up better efficiency to acidic
wastewater treatment. According to above conditions, researcher found the optimum shells volume, exposure time to
check the correctness of the experiments about increasing pH and reducing color, iron in wastewater. Oyster shells have
implications in environmental protection, treatment cost saving and contributing the diversity of natural resources.

Keywords: Oyster shells; pH; CaCO3; neutralizing.

1. INTRODUCTION emissions of SO2, NOx came from some industries (Jung et

Vietnam accompanied with many marine advantages
including a coastline of over 3260 km. Besides that, there
are many lagoons which are suitable for aquaculture
industry. The climate and terrain are also favorable for its
development. These advantages are appropriate for
aquaculture industry in general and bivalve mollusks in
particular. According to Vietnam association of seafood
exporters and producers, aquaculture production statistic
of 2 pieces - mollusks in 2012 reached 26240 tons/year (an
increase of 1.22 times in comparison with 2009). Amongst
that, in 2012 oyster production tends to increase to 7347
tons/year (Vietnam association of seafood exporters and
producers). However, this also lead to an increase in the
amount of waste oyster shells which were discarded into
the environment from industrial processing, bars,
restaurants.... In regard to a research of Marine Research
Institution: "For each ton of oyster meat production, there
are 8 tons of shells are disposed, the volume of discarded
shells in 2012 was 6531 tons/year (Research institute for
Marine fisheries). This waste which discarded into the
environment caused unpleasant smell due to the disposal
of oyster meat leftover parts. The process of decomposing
oyster flesh created different types of gas including:
Amine, NH3, H2S which caused severe impact to
environment and human health.
In order to remedy this situation, many Korean
researchers used oyster shells as a sort of building
material (Yoon et al., 2003; Kristy Noel Kelley., 2009)
experimental results demonstrate that the oyster shells are
effective and can be a replacement of sand for reducing
the intensity compression. For environmental remediation
purpose, oyster shells are effective in controlling
eutrophication (Kwon et al., 2004; Park et al., 2008). In
2012, South Korea conducted several projects which
concerned with the accessibility of oyster shells to handle
al., 2012). In Vietnam, a study by Bui Truong Tho: "Use of
agricultural waste, wastewater treatment aquatic
activities" (Tho, Bui Truong), which use shredded coconut
combine clam shells, oyster shells in domestic wastewater
treatment by reducing the contaminants through the
filtering process has showed satisfactory results.
The objective of this research was to examine the usable
ability CaCO3 component in oyster shells for wastewater
treatment in metal ware craft villages. Specifically, the
paper clarifies the ability of oyster shells in changing the
pH value of acidic wastewater treatment through jar test
experiments and to find out the optimum conditions for
the process. Based on that, it was essential to determine
the relationship between pH values and color, iron content
processing capabilities of the effluent from metal ware
craft village Thanh Thuy - Thanh Oai - Ha Noi.
2. RESEARCH METHOD
Oyster shells on one hand are considered as left-over from
the fishery industry; however, with CaCO3 component
made up to 95%, oyster shells are able to be recycled as a
source of water treatment process in metal ware craft
village.
In regards to the findings from some previous science
researches on characteristics and natures of oyster shells, it
was indicated that waste oyster shells are similar in
composition with limestone (Jung et al., 2005):

1
 % Furthermore, calcining kiln which was used in the
subsequent experiments was not the spinning type, so it
60
SiO2 was critical to use larger shells size for calcinating. If the
shells sizes were small, the material would fill all voids,
40 Al2O3
then they would be separated from the heat which could
Fe2O3 make the calcining-shells well done or rare.
20
CaO In the other hand, from 1 unit volume of bulk density, the
0 MgO dimension of oyster shells is inversely proportional to the
Waste oyster interface and material weight. The interface between solid
Jungsun Ignition Loss
shells and liquid counts base on one unit of weight, often noted
limestone by m2/g, and it affect to the reaction timing
(http://www.richardanderson.me.uk/keystage4/GCSEC
Figure 1: Composition of waste oyster shells and Jungsun hemistry/images/largeparticles.gif).
limestone

In the scope of this report, the research object was to use

oyster shells as instrument in treating acidic waste water.
The water treating experiment was conducted by using
neutralize method with oyster shells. The preliminary
treatment process for oyster shells in order were: wash,
dry, heat. Samples from the process were gathered and
distinguished by lattice screen, which divided into three
types based on size: (type 1: from 1-2 cm, noted as L1; type
2: from 2-5 cm, noted as L2; type 3: original size (>5 cm),
noted as L3). Afterwards, oyster shells were calcinated in Figure 2: Dimensions affect to the interface
kiln, then allocated in dry-cabinet and cooling to reach
room temperature.
Temperature and timing of calcination process
Based on the method of neutralizing, acidic waste water
had to be neutralized in order to bring pH to about 6.5 to After choosing the size, it was essential to treat the shells
8.5, before discharging into receiving resources or by heat to form the activation properties of oyster shells.
technology used for further processing. Wastewater The changes of temperature and calcination timing were
neutralization could be achieved in which acidic water important, which determined the raising of pH index by
was purified by using materials which were capable of using oyster shells.
neutralization. The calcination process was conducted as:
The contents of this report demonstrate the ability of CaCO3 CaO + CO2
oyster shells to increase pH in wastewater treatment for
metal ware craft villages. Through Jar test experiments, The calcination process is endothermic reaction with main
the optimum results for the following conditions were component is CaCO3. The activation energy for this
established: size shells, burning time, burning reaction is calculated by the following equation, (Jung et
temperature, shells volume, exposure time to improve al., 2012):
processing efficiency.
CaCO3(s) CaO + CO2 (1)

3. EXPERIMENT RESULTS = (1 ) (2)

( )
Dimension of shells = (3)

( )
The dimension of oyster shells is highly correlated to the = (1 ) (4)
ability of increasing pH. From 3 grain sizes collected after
Where: x = mass of waste oyster shells and limestone,
screening (L1, L2, L3), it is essential to choose the optimum
type for using oyster shells in treating wastewater as k = reaction rate,
saving the energy cost for calcining process.
X = conversion,
The grain size is correlated to the void ratio. Void ratio
n = reaction order,
from the material is directly proportional to capability of
diffusing oxygen into water which contributes the A = pre-exponential factor,
treatment process. Void ratio (%): the void volume
contained in one unit volume of material. If Vr is Ea = activation energy,
considered as void volume and Vv is considered as R = gas constant,
materials volume then:
T = absolute temperature.
V
v r (Lu, Phung Van., 2008) The higher the temperature, the greater amount of heat
Vv collected, and the amount of CaO, CO2 had increased.
While CO2 had been escaping, the material became light
Where: Vr = Vv V and forming voids. The voids contributed to increasing
the interface area between CaO and wastewater, thereby
V: the materials volume in state of totally solid (liter)
the neutralizing reaction carried out acidic waste sources.
Vv is always fixed, Vr is directly proportional to V However, if the calcination temperature was too high,

2
shells would crack, then the small pieces would easily pH
sediment. 8
The capability of increasing pH by the sample in different 7
points calcination temperature, with calcination time 1h 6
5
and 1.5h was shown in figure 3; 4. 1h
4
3 1,5h
pH
2
8 1
7 T=300 C 0 minutes
6 10 20 30 40 50 60
T=450 C
5
4 T=600 C
3 Figure 5: pH values at 6000C calcination temperature in 1 hour
T=750 C and 1.5 hours timing.
2
1 T=850 C Application for finding the optimum volume in
0 wastewater treatment at Thanh Thuy craft village
10 20 30 40 50 60
minutes
Wastewater samples were taken from 4 villages: Rua Ha,
Gia Vinh, Rua Thuong, Tu Am. The analysis in
Figure 3: pH values at different temperatures with 1 hour characteristics of samples was shown in the following
calcination table:
pH Table 1: Analysis of wastewater input parameters

8 Vietnam
7 T=300 C
Standards
6
T=450 C Parameters Unit M1 M2 M3 M4 (40:2011
5
T=600 C (column
4
B)
3
T=750 C
2
1 T=850 C Temperature
0C 28 27 26 26 400C
0 (0C)
10 20 30 40 50 60
minutes

pH 2,10 2,09 2,15 2,05 5,5 9

Figure 4: pH values at different temperatures with 1.5 hours
calcination
Color Pt-
Based on the testing experiment, the aptitude of refreshing 682 894 778 822 150
acidic wastewater of oyster shells increased along with Co

increase in calcination temperature and timing. This result

was apposite with the concept which cited above.
Specifically, pH in both figure were directly proportional
to the heat while calcination. However, when reached to
the definite temperature (from 6000C), pH value in
wastewater was stable, only slightly increased. For 750 0C
and 8500C, pH reached its highest value. However, the
change in pH value was only 8% while compared to
6000C, the change was very significant - 30%.
Furthermore, the stability of shells shape was very low
when temperature reached 7500C and 8500C, it had many
disruption lines, and created many small pieces which
were difficult to collect. On the other hand, the shells
shape was relatively stable at 3000C, 4500C, however, the
pH value was very small in changes. The above
weaknesses were solved at temperature of 600 0C, with the
ability to increase pH value to 6.25 in 1 hour (pH equals
6.75 in 1.5 hours) and limited the lime sediment. In
conclusion, it was optimal to choose the calcination
temperature of 6000C.
For 6000C, the ability to increasing pH value in 1.5 hours
(pH equals 6.75) was not different comparing to
calcinating in 1 hour (pH equals 6.25). Thus, it was
appropriate to choose the timing as 1h for energy cost
saving.
Iron mg/l 580,46 670,12 594,89 621,25 5
With the input parameters above, if wastewater from craft
villages was directly discharge to the environment, it
would lead to heavy pollution. This is due to the fact that
all the above parameters were excess the allowed
standards for environment-discharging wastewater. Thus,
in order to vindicate the effectiveness of oyster shells, it
was essential to find the optimal volume of shells as well
as the optimal exposure time based on changes in pH.
Optimal volume of shells
Within the same volume of wastewater, the greater the
amount of shells, the faster the reaction takes place.
However, it is not ideal if using too many oyster shells.
This would lead to the waste of resources and increase the
cost of operation. The optimal results of oyster shells
amount for 1 liter of village's wastewater are shown in
Figure 6.

3
 pH
7 observed that the pH growth performance increased
6 6.07
5 5.8 6.05
4.92
4 4.21
pH
3
2 From the optimal conditions of material: Shells size was
1
0
125 250 500 750 1000 grams
Figure 6: pH values for 125, 250, 500, 750, 1000 grams
With input pH value equals 2, pH value changed after
exposure to increasing amounts of oyster shells from 125g-
500g. At 125g, pH after about 60 minutes exposure time
reaches 4.21; while at 500g, pH value reached 5.80; the
difference between two values was 1.59. Meanwhile, with
the same period of exposure time the volume which had
the highest pH value reached was 1000g. However, the
difference in pH value at the shells weight value of 500g,
750g, and 1000g were relatively small. In particular, the
pH value at 750g oyster shells was larger than 0.25
compare to pH value at 500g, also similar to the difference
of only 0.02 with 750g and 1000g. The difference between
the two intervals of pH value above was 12.5 times, which
suggested that an increase in the shells volume of 250g
would not lead to the same efficiency. Therefore, it was
critical to say that the optimal parameter of usable shells
volume for 1 liter of wastewater was 750g.
Exposure time
The testing result showed that pH value tended to rise
along with the rise in exposure duration.
C (Khuong, Nguyen., 2002)
Vtb mol / ls
t in 2014, oyster shells had aptitude for iron ion absorption.
Where:
Vtb: the average speed (mol/ls)
C C1 C2 : concentration variability (mol/l)
C1: initial concentration (mol/l)
C2: equilibrium concentration (mol/l)
t : time (s)
The equation above showed that exposure time related to
velocity and variety of concentrations.
Figure 7: Performance of increasing pH in periods of time
In the period from 10 to 30 minutes early, the performance
of pH growth had increased exceedingly (from 60% to
66%). After that, in the period from 30 to 60 minutes, this
performance had just slightly improved (from 66% to
67%). The last period (from 60 to 70 minutes) had
inconsiderably. Therefore, it was specifically to say that
the optimal exposure duration was 60 minutes.
Assessing the effects of iron treating
from 2 to 5 centimeters, calcination temperature equals
6000C, calcination timing was 1 hour, exposure time was
60 minutes and the input parameter:
+ pH = 2
+ Color: 786 Pt Co
+ Iron content: 597,54mg/l
Researcher use 3000g of the material to treat 4000
milliliters acidic wastewater.
As waste water was taken from the metal ware craft
village, the iron value in the samples accounted was high
component account for a large amount. The iron ions had
existed as Fe2+, therefore the color of wastewater was
green. But according to the experiment, color of
wastewater samples was turned into yellow, which could
respond by the change of iron ion into Fe3+. The reaction
took place according to the formula:
4Fe2++ O2 + 2H2O + 4Ca(OH)2 4Fe(OH)3 + 4Ca2+
The iron ion Fe3+ easily settled to the bottom, and the
samples turned to yellow. But the reaction above had
conditions to completely happen, one of those was pH.
The reaction was bidirectional, while pH value was high,
that formula above would happen more easily.
Furthermore, in regards to researches by Chayapat
Tabtong, Sinsupha JuiJuijerm in 2009; Md. Atiqur Rahman
et al.in 2008; Woo-Seok Shin, Ku Kang, Young-Kee Kim
Iron ion absorption capacity of oyster shells was
determined by the formula:
V .(Ci Ce )
Qe .103 , mg / g (Davis T.A., 2000)
m
Where:
V: volume of solution (l)
Ci: initial concentration (mg/l)
Ce: equilibrium concentration (mg/l)
m : amount of adsorbent (g)
According to the theories above, the experiment had
shown the capability of oyster shells in treating iron
through figure 8 and 9:
pH
7
6
5 Initial pH values
4
3 pH values after
2 exposure
1
0 minutes
5 15 30 60
Figure 8: pH values through exposure periods
4
 and duration of exposure. Based on that, we evaluated the
600 70 % ability to handle the iron content, the true color in
60
wastewater samples by using oyster shells. In general, the
500 research group came up with several conclusions:
50
400 + Shells size from 2 - 5 cm was optimal for scalability of
pH.
iron content (mg/l)

40
300 + 6000C calcination temperature in 1 hour was the
30 iron content optimum time to keep the oyster shells shape during
200 process.
20

100 processor + Optimal exposure time (processing time) was 60

0 0
5 15 30 60
Figure 9: Iron contents and performances
According to these charts, while pH value reached to 5.05,
iron treating performance was just 10%, comparing to 60%
while pH value reached to 6.09. This experiment indicated
the relative between pH and iron content, moreover,
including oxygen diffusion into water and the exposure
time.
Assessing the effects of color treating
Due to the color variation during the experiment, the
color values were measured after 60 minutes exposure
time. The experiment was carried out after filtering. The
result was shown in figure 10.
600
500
400
Color
10
performance minutes.
Research showed that oyster shells were usable in
minutes wastewater treatment in craft villages. The activation of
oyster shells after firing sewage treatment is a new
method in recycling solid waste, creating beneficial
products for production, lessens environmental problems
caused by aquaculture along with cost savings and avoids
environmental impacts during extraction of natural
resources such as limestone.
Recommendations
Due to limited testing and laboratory conditions,
assessing the ability to handle pH and color, metallic iron
content of oyster shells as well as the factors affecting
treatment efficiency are not in the scope of this paper .
Areas of this study and applications of oyster shells in
wastewater treatment were a new field in Vietnam. To be
able to deploy the applicable results in real environment,
further researches are required, as well as researches must
be conducted in a larger scale. The researchers should
% further issues: the institution, policy, technology, human
70 resources, finance and public awareness for recycling
60 oyster shells can be used more commonly to save natural
resources which are increasingly depleted.
50
During the study, analyzing the parameters had shown
40 the property affecting the processor efficiency is porosity

300 Color
30
materials. However, due to the lack of time, it was
200
unavailable to introduce the concept of a new group,
20 formula. Hopefully in the future if all conditions are met,
Processor
100 performan the project can be expanding to focus more with optimum
10
ce color temperature for broken oyster shells and chemical
0 0 adsorption as well as research by surface adsorption
5 15 30 60 minutes handling of hazardous materials for reuses cost savings
and effective treatment of CO2 released from the kiln.
Figure 10: Color values and performances in removal color

At 60 minutes exposure time, the performance reached

to over 60%, which was the peak of the line. The REFERENCES
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