THE USE OF CLAY AS ADSORBENT AND COAGULANT AID IN

TEXTILE WASTEWATER TREATMENT

Andita Rachmania Dwipayani1, Suprihanto Notodarmojo2, and Qomarudin Helmy3
Graduate Program of Environmental Engineering
Faculty of Civil and Environmental Engineering, Institut Teknologi Bandung
Jl. Ganesha No. 10, Bandung 40132
1
andita.rachmania@gmail.com, 2suprihanto@ftsl.itb.ac.id, 3kihelmy@yahoo.com

Abstract: There are two sub researches that are conducted in this research, both researches were done batch at
the room temperature. The first sub research is analysis of adsorption capability of clays for organic
compounds removal (COD) from textile wastewater. In this research, the variables that examined were
wastewater pH level, dosages of clays, and contact time on adsorption process. The wastewater that used were
originated from effluents of textile production units with concentration of COD approximately 230-285 mg/L.
The purpose of this research was to obtain the optimum conditions for the ability of both kinds of clays to
remove COD parameter of waste water. After the optimum condition was obtained, analysis then carried out to
the determination of adsorption kinetics for COD removal, using Langmuir and Freundlich isotherm models.
Optimum conditions on the use of Arcamanik and Dago clays were at pH 7 and the dose of clays of 15 gr/L and
30 mg/L. COD removal reaches its stagnant level at the contact time of 120 minutes. At this condition, COD
removal for Arcamanik and Dago clay reach 48.5% and 26.65%. Factors that affect the clays capability as
adsorbent are associated by the morphological properties of clay. The second sub research is clays potential as
coagulant aid for COD removal. The research variables that were conducted were variation of dosages of clay
and wastewater pH level. For the use of 30 mg/L of alum coagulant, the addition of 30 mg/L of Arcamanik clay
was able to improve the COD removal efficiency from 8.95% to 13.43%, while the use of Dago clays generate
the COD removal to 16,98%. But this COD removal efficiency level was still lower than one with the use of 40
mg/L of alum, that is 17.9%.
Keywords: textile wastewater, COD, clays, adsorption, coagulant aid.

INTRODUCTION
Textile industry is one of the industries that has rapid development in Indonesia.
Textile industrys production process consists of the process of desizing, bleaching, drying
and coloring. Textile fabric staining process produces waste that has been known contains
chemical compounds, surfactants, dissolved solids, and probably contains heavy metals like
Cr, Ni, and Cu (Kannan and Sundaram, 2001).
In general, wastewater treatment can be conducted physically, chemistry, and
biologically. But chemical, physical, and biology processes which commonly applied often
become less effective because the more complex the waste that is produced and the high
operational cost (Sugiarto, 2002 in Hadiwidodo, et al., 2009).
One of the common applications of physical treatment is the coagulation and
flocculation process. Coagulation and flocculation processes include the addition of chemical
compounds and agitation that make colloidal particles destabilized which form flocks that are
capable to precipitate. The chemical compound that is added called coagulant.
To improve the performance of the process of coagulation, the common thing that
usually done is the addition of other compounds, called coagulant aid. Coagulant aid that
commonly used are chemical compounds of the polymer. Beside of its function to improve
the coagulation performance, the addition of coagulant aid also aims to reduce the use of
chemical coagulant (alum, lime, ferro sulphate) required. However, the most abundant
polymer compounds used as coagulant aid have a high selling price in the market.
One way to improve the coagulation performance is to do a combination with other
process, such adsorption. Adsorption is the process of centralizing the molecule or ion
1

adsorbate on surface layer of adsorbent, either physically or chemically (Muhdarina, et al.,

2010). Adsorption is a process that has good prospects in the textiles wastewater treatment
process (Robinson, et al., 2001; Kamel, et al., 1991; in Mumin, et al., 2007).
Research on combination of coagulation-adsorption process has been done, one
example by Shen and Chaung (1998). In this study, they use polydially dimethyil ammonium
chloride (PPDAC) coagulant and activated carbon adsorbents of 100 mesh-size. Conclusions
of this research was that the addition of carbon adsorbents on the coagulation process proved
effective in the removal of dissolved organic carbon compounds because each process is able
to cover each other's deficiencies. Organic compounds that were removed by the process of
coagulation were compounds with high molecular weight and have a negative charge. While
the use of activated carbon more effectively to adsorp compounds with small molecular
weights and are uncharged.
This research aims to find alternative materials that can be used as substitution for
chemical coagulant aid, especially in removal of organic compound in wastewater. One
material that has abundant availability in nature with relatively low price is clay. In the use of
clay for wastewater treatment, clays are generaly classified as adsorbent, because they have
adsorption ability due to their surface area (Al-Jlil and Alsewailem, 2009; Errais, et al., 2012;
Liu and Zhang, 2007).
The type of clay that commonly used as nano-adsorbent are montmorilonite/smectite
and kaolinite (Liu, et al., 2007). Previous researched that conducted by Adebowale, et al
(2006) about adsorption of metals ion by clay showed that adsorption of metals increased by
the addition of initial concentration of metals, pH, and adsorbent dosages (Al-Jlil, et al.,
2009).

METHODOLOGY
This research consists of two sub researches which in practice include several stages,
they are: the initial textile waste characterization and analysis of morphology of clays, clay
adsorption capability analysis, and analysis of the ability of clay as a coagulant aid.
Initial characterization of the textile waste and morphologic analysis of clays
This stage consists of analysis of mineral and morphology of clays, and the initial
textile wastewater quality. Parameters measured for wastewater quality are mentioned in
West Java Decree No. 6/1999 on quality standards for textile industry wastewater. These
parameters include: BOD, COD, TSS, Total phenol, Chromium (Cr), oil and grease, and pH.
While one example of the analysis of the mineral content and morphology of clays is
conducted from XRD and BET surface analysis.
Adsorption Analysis of Clays
The process of adsorption was done in batch for both kinds of clays. The adsorption
analysis conducted through the variation of pH level of wastewater, dosages of clays, and
contact time, those are done gradually. At first, clays used were pounded and sifted so
acquired the clays in desired size. The purpose of this analysis is to determine the optimum
conditions of the adsorption capacity for both kinds of clays for the removal of COD of
textile wastewater.
Analysis of clays after adsorption process
At the end of adsorption process, the clays that were used then analysed their
morphological and composition to be compared with their initial condition before treated as
adsorbent. Morphological analysis of clays performed with SEM (Scanning Electron
Microscopy) and FTIR (Fourier Transform Infrared Spectroscopy).

Analysis of clays as coagulant aid

This study aimed to compare the removal efficiency of COD with and without the
addition of clay into the coagulation system. Research variables taken include: variation of
clays used and the variation dosages of clays. Of these variables, the optimum conditions for
the use of clays are then compared to the one without the addition of clays.
Data Analysis
To describe the mechanisms of adsorption, there are two types of isotherm models that
can be used: Langmuir and Freundlich isotherm (Fair, et al., 1968). Langmuir isotherm form
displayed on the equation. 1 while the equation for Freundlich isotherm is shown on
equation. 2.

=
log

+
= log

(equation. 1)
log

(equation. 2)

q is the mass of a substance per unit weight of adsorbent (mg/g), Ce is the concentration
of a substance in equilibrium point, KL is the Langmuir constants, Kf is the Freundlich
constants, and is a factor of heterogeneity. Freundlich isotherm has been used extensively
by researchers as a simple way to analyze the adsorption of organic compounds (Joseph, et
al., 1993).

RESULTS AND DISCUSSIONS

Wastewater quality
The wastewater that used came from the effluents of a production unit of the textile
industry in Bandung (PT. X). Analysis of the quality of the initial waste were done based on
the raw quality of textile waste that is set in Governor of West Java Decree No. 6/1999.
Results of the analysis are shown in Table 1.
The high values of organic parameters, namely COD and BOD indicates that the waste
water has a high organic content, which is possibly derived from a substance used in the
production process. Aside from the process of coloring, the high concentration of organic
polluters come from wet process in the production of fabrics, which include the desizing,
bleaching, and scouring processes (Komarawidjaja, 2007).
Table 1. Wastewater Quality Result
No
1
2
3
4
5
6
7

Parameters of
Analysis
BOD
COD
TSS
Fenol
Total Chromium (Cr)
Oil & Grease
pH

Unit

Method

Maximum
Level*

Analysis Result

mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
-

SMEWW 5210-B
SMEWW 5220-B
SMEWW 2540-D
SMEWW 5530-C
SMEWW 3500-Cr
SMEWW 5520-D
SMEWW 4500-H+

60
150
50
0.5
1.0
3.0
6.0 9.0

125
281.6
102
0.214
0.088
12.4
7.38

*Quality standards refers to Governor of West Java Decree No. 6/1999

The characteristics of adsorbent

The clays characteristics analysis includes morphological analysis and mineral content
of the clay. The XRD analysis for the clays mineral composition results shown in Tables 2
and 3.
Table 2. Mineral Composition of Dago Clay.
Mineral Composition
Quartz
Kaolinite
Muscovite

Chemical Formula
SiO2
Al2Si2O5(OH)4
(K, Na) Al2(Si, Al)4O10

Table 3. Mineral Composition of Arcamanik Clay

Mineral Composition
Kaolinite
Albite, calcian, ordere
Muscovite
Cristobalite
Montmorillonite

Chemical Formula
Al2Si2O5(OH)4
(Na, Ca) Al (Si, Al)3O8
(K, Na) Al2(Si, Al)4O10
SiO2
CaO2(Al, Mg)2Si4O10(OH)

Clay mineralogy is typically monotonous: kaolinite, gibbsite, hematite, goethite,

maghemite and Ti minerals (mainly ilmenite and anatase) are the prominent mineral phases
in the clay fraction (Schaefer, et al., 2008). It can be seen that in general, both types of clay
used have a type of kaolinite minerals. The kaolinite minerals are known for its ability to
form stable dispersions and to improve the properties of the material (Kogure, et al.,2010).
Kaolinite group has properties such as: easily to expands or shrinks, and difficult to
destroy (stable) (Notodarmojo, 2005). Besides kaolinite group, there is also the content of
montmorillonite which belong to the group of minerals smectite. Smectite minerals have a
negative charge which causes minerals are very reactive (Nilawati, 2013).
The surface area of adsorbents is one of the important parameters for the interpretation
of the sorption mechanism of organic compounds (Jonge and Mittelmeijer-Hazeleger, 1996).
The large surface area of adsorbent enhance the possibility of sorbate to be adsorbed through
the surface of adsorben, thus may increase the adsorbent activity (Nilawati, 2013).
Determination of the surface area of adsorbent was done with BET (Brunauer-EmmettTeller) analysis method towards both of clays that were used. The analysis result shown on
Table 4.
Table 4. Surface Area, Volume, and Diameter of Dago Clay and Arcamanik Clay
Parameters
Surface area (m2/g)
Total pore volume (cc/g)
Average pore diameter

Dago Clay
35.987
9.981 x 10-2
For pores smaller than
4204.9 * (diameter)
1.10936 x 102

Arcamanik Clay
84.923
1.629 x 10-1
For pores smaller than
2257.1 * (diameter)
7.67151 x 101

*1 = 10-7 mm

From Table 4, it can be seen that surface area of Arcamanik clay is wider than Dago
clay, which accompanied by smaller size of average pore diameter. This result correspond
with the theory stated by Notodarmojo (2005), that the more subtle or the smaller the
diameter particles of a material, the wider the specific surface area.

The influence of pH to the adsorption of the organic compounds

This experiment carried out analysis of the removal efficiency of organic substance
parameters (COD) of the variation of pH of wastewater, at pH 4, 5, 6, 7, 8, and 9. For both
types of clays, Adsorbent added as much as 2.5 gr/L. The process of adsorption was done in
batches for 120 minutes. The results shown in Figure 1.
50

Efficiency (%)

40
30

Arcamanik
Clay
Dago Clay

20
10
0
3

6 pH 7

10

Figure 1. The Influence of pH on The COD Removal Efficiency in Textile Waste Water
in Adsorption Process Using Clays (Dago and Arcamanik Clays).
On the use of Arcamanik clay, pH level of wastewater variation of 4, 5, 6, 7, 8, and 9
generate COD removal efficiency of 32.76%; 32.76%; 35.51%; 43.96%; 38.36%; and
35.56%. While the use of Dago clay generate the COD removal efficiency towards the same
variations of pH are: 27.74%; 19.4%; 19.4%; 47.19%; 36.07%; and 11.06%.
This result are correspond to some adsorption researches, one example were conducted
by Liu and Zhang (2007), where adsorption with montmorillonit clay generate the highest
COD removal on neutral pH. Adsorption capacity decreases with the increasing pH level,
except on neutral pH (Liu and Zhang, 2007). The research conducted by Scrudato and Estes
(1975) showed that montmorillonite had the highest adsorption capacity on pH level of 7.5
(Al-Jlil and Alsewailem, 2009).
Almost all of the adsorption process are affected by the pH of the solution (Mahmud,
2012). This happens because the pH of the solution and electrochemical properties affect the
surface charge of the particles or colloids. The changes of pH could affect the natural
condition of sorption process, because ionization of organic compounds depends on pH level
of wastewater, which then implicate to the solubility of organic compounds in the solution
(Maoz and Chefetz, 2010). However, the optimum pH is very specific to each compound, so
that solution with low pH is not always certain to produce a good adsorption process.
The influence of the dosage of clays to the adsorption of organic compounds
The experiment on the influence of adsorption clays dosages done on the pH optimum
that obtained from the results of previous experiments. Research done in batch for 120
minutes with a dosages of clays of 2.5; 5; 10; 15; 20; 25; 30; and 35 gr/L. Analysis were done
towards the adsorption capacity of clays and COD removal efficiency. Results of the
experiment are shown in Figure 2.
For the use of Arcamanik clays, dosages variation of clay of 2.5; 5; 10; 15; 20; 25; 30;
and 35 gr/L generate COD removal efficiency of 29.11%; 33.82%; 35.3%; 37.7%; 38.59%,
and 39.38%. Optimum results achieved on the use of clay as much as 15 mg/L. While in the
use of Dago clay, adding dose of 2.5; 5; 10; 15; 20; 25; 30; and 35 gr/L generate COD
removal efficiency of 29.72%; 30.62%; 32.56%; 36.18%; 36.99%; and 37.74%.

COD Removal Efficiency (%)

41
39
37
35
33
31
29
27
25
0

10

15

20

25

30

35

Dosages of Clay (gr/L)

Arcamanik Clay

Dago Clay

Figure 2. The Influence of Clays Dosages on The COD Removal Efficiency

The use of both clays gave similar result that the addition of dosages of clays were
proportional to the adsorption effeciency. The more clay were added, the higher organic
removal efficiency. This happened because the amount of adsorption sites were increase with
the higher adsorbent dosages, which resulting to the higher sorbate removal efficiency
(Mumin, et al., 2007).

12

60

10

50

40

30

20

10

0
30

60

90

120

150

Efficiency (%)

Adsorption Capacity (mg/g)

The influence of the contact time to the adsorption of organic compounds

In an adsorption process, process will continue to take place whenever the equilibrium
state has not reached. Therefore, to determine the equilibrium distribution between
adsorbents with adsorbate, the experiments conducted with variations of the contact times.
Determination of equilibrium state was done to predict when an absorber material reaches its
saturation level so that the process of adsorption had ended (Nilawati, 2013).

180

Time (minutes)
Adsorption Cap: Arcamanik Cl

Adsorption Cap: Dago Cl

Eff: Arcamanik Clay

Eff: Dago Clay

Figure 3. The Influence of Contact Time to The Adsorption Capacity and COD Removal.
On this experiment, analysis of adsorption conducted on optimal conditions that had
been acquired earlier (pH=7, field clay dose = 15 gr/L, and brown clay dose = 30 gr/L). On
each of these conditions, analysis then conducted against contact time variations of 30, 60,
90, 120, 150, and 180 minutes. The analysis result of the effect of contact time displayed on
Figure 3.

Figure 3 shows that the longer the contact between the adsorbate with the adsorbents,
the more adsorbate adsorbed. This can be seen from the increase in capacity in both
adsorption clays are used. For both types of clays, the optimum point where COD removal
efficiency reaches its equilibrium point. The time to reach equilibrium state are different on
every adsorption process, it is influenced by the interaction types happen between adsorbent
and adsorbate (Wicaksono, 2012). On the use of Arcamanik clay, the equilibrium point
reached at the 120th minutes, as well as the use of Dago clay.
For the use of Arcamanik clay, the efficiency of COD removal in 30, 60, 90, 120, 150
and 180 minutes are: 35.23%, 37.14%, 42.85%, 48.57%, 48.57%, and 48.57%. The
adsorption capacity of clays towards the variation of contact times respectively are: 8.27;
8.72; 10.06; 11.4; 11.4; and 11.4 mg/g. As for the use of Dago clay, removal efficiency of
COD at 30, 60, 90, 120, 150 and 180 minutes are: 24.13%; 24.96%; 27.14%; 27.9%; 28.58%;
and 29.11%, and the adsorption capacity are: 5.67; 5.86; 6.37; 6.55; 6.71; and 6.84 mg/g. The
equilibrium state for the use of both types of clays were estimated happened on 120th
minutes.
Determination of adsorption isotherm model
Determination of adsorption of organic compounds isotherm model are conducted in
optimum condition for each clay. Analysis of Langmuir follow an isotherm equation on
equation 1. From a linear curve that plots relationship between the C/m versus C, it can be
determined the value of the slope of the Qm (slope) and KL from the intercept of the curve.
The result of Langmuir isotherm model for each of the clays are shown in Figure 4.
0,13
y = -18,62x + 0,241
R = 0,986

0,12

1/q

0,11
1/q

0,2
0,19
0,18
0,17
0,16
0,15
0,14
0,13
0,12

0,1
0,09
0,08
0,006

0,007
1/Ct

0,0054

0,008

y = -76,77x + 0,606
R = 0,996

0,0056

0,0058
1/Ct

0,006

0,0062

(a) Arcamanik Clay

(b) Dago Clay
Figure 4. Langmuir Isotherm
0,86

1,1

0,84
y = -1,364x + 3,898
R = 0,996

y = -2,768x + 6,986
R = 0,999

0,82
Log q

Log q

1,05
1

0,8

0,78

0,95

0,76
0,74

0,9
2,05

2,1

Log Ct

2,15

2,21

2,2

2,22

2,23
2,24
Log Ct

2,25

2,26

(a) Arcamanik Clay

(b) Dago Clay
Figure 5. Freundlich Isotherm
The Freundlich equation is an empirical equation employed to describe heterogeneous
systems, in which it is characterized by the heterogeneity factor 1/n. (Wicaksono and Effendi,
7

2012). Freundlich isotherm equation is obtained by plotting value of log q and log Ce. The
results can be seen in Figure 5.
5 While the values of KF, 1/n and R2 of each Freundlich
isotherm model can be seen in Table 5.
Table 5. Adsorption Parameters obtained From Langmuir and Freundlich Isotherm
Isotherm.
Clays
Arcamanik
Dago

Isoterm Langmuir
KL
Qm
R2
(L/mg)
(mg/g)
-0.01294
01294
4.149
0.986
-0.00789
00789
1.65
0.996

Isoterm Freundlich
KF
1/n
R2
1/n
(mg/g)/(mg/L)
7.9x103
-1.364 0.996
9.68x106
-2.768 0.999

In describing the mechanisms of adsorption of COD using field and brown clays,
Freundlich isotherm model was able to describe
describe it better than the Langmuir isotherm model.
It is visible from the coefficient of determination (R2) Freundlich isotherm model is more
close to the value 1 rather than Langmuir isotherm.. A negative value for the KL on Langmuir
isotherm showed that experimental data are obtained on the process of adsorption of COD
using field and brown clays does not have compatibility with Langmuir isotherm model.
The value of 1/n that is less than one indicates that the adsorbent has molecules with
saturated adsorbate when descending on the adsorption energy density of the surface. This is
because the price of 1/n is related to the magnitude of the forces (driving force) adsorption
and the distribution of energy sites on adsorbents (Karanfil, et al.,, 1999 in Mahmud, 2012).
SEM and FTIR results
SEM (Scanning Electron Microscopy) analysis were done with the magnification of
20,000 times. The SEM result of the Arcamanik clays before and after adsorption process are
shown on Figure 6,, while Dago clays shown on Figure 7.
The morphological changes of clays before and after adsorption process happened due
to the organic compounds that filled the pores of the adsorbents. The final morphology of
both clays shows that agglomeration on the surface of particles has happened, so tthat the
pores of clays that were initially empty, became filled by organic compounds. The filling of
the surface of adsorbents occured because of physical and chemical bonds between clays and
sorbate.

(a) Before Adsorption

(b) After Adsorption

Figure 6. Morphology
ology of Arcamanik Clays by SEM with 20,000 Magnification

(a) Before Adsorption

(b) After Adsorption

Figure 7. Morphology of Dago Clays by SEM with 20,000 Magnification

FTIR (Fourier Transform Infrared Spectroscopy) analysis was conducted to identify
materials and the presence of functional groups in clays. The FTIR result for Arcamanik
clays, before and after adsorption process are shown on Figure 8.a and 8.b.
Vibration on wavenumbers 2923.56 cm-1; 1346.07 cm-1; 1411.64 cm-1 shown on Figure
8.a gives information about the presence of C-H bonds (Skoog, et al., 1984). Stretch
vibration on 3189.68 cm-1 and bend on 1558,2 cm-1 happened because of the presence of N-H
bond (Silverstein, 1998). The double bond of C=C and O-H bond were detected by the
vibration on 1643.05 cm-1 and 3625.52 cm-1, while stretch vibration on 2553.29 cm-1
wavenumber shows the presence of S-H bond (Coates, 2000).

Figure 8.a Infrared Spectrum of Arcamanik Clay before Adsorption Process

Figure 8.b Infrared Spectrum of Arcamanik Clay after Adsorption Process

FTIR result of Dago clay, before and after adsorption process shown on Figure 9.a and
9.b. Vibration on wavenumbers 2854.13 cm-1; 2923.56 cm-1; and 2688.28 cm-1 shows the
presence of O-H stretch bond. The presence of C=O amides and N-H amines shown by the
vibration on 1639.2 cm-1. Vibration on 782,95 cm-1 wavelength indicates the S-O bond with
the sulfonate functional groups (Glagovich, 2013).

Figure 9.a Infrared Spectrum of Dago Clay before Adsorption Process

10

Figure 9.b Infrared Spectrum of Dago Clay after Adsorption Process

According to Wan Ngah, et al (2008), if not much changes in wavenumbers happens
after the adsorption process, or no appearance on new waves peak, then the adsorption
mechanism happened phisicaly (Mahmud, 2012). Comparison between the existence of the
wave peaks at the beginning and end of the adsorption on the use of Arcamanik clay (Figure
8.a and 8.b), shows that there are similarities between the two forms. However, there are new
peaks after the adsorption process. The same phenomena shown with the use of Dago clay.
The emergence of these new peaks showed bonds between the adsorbate and the
functional groups of adsorbent (Wan Ngah and Hanafiah, 2008 in Mahmud, 2012). The peak
intensity of the Arcamanik clay after adsorption showed little displacement and substantially
lower than that before adsorption process. This happens due to the involvement of functional
groups of adsorbent in the bond between adsorbate and adsorbent (Wan Ngah and Hanafiah,
2008 in Mahmud, 2012).
The result of FTIR analysis obtained correspond to the isotherm adsorption model
result in this experiment. The isotherm model that more accurately described the adsorption
process of organic compounds using both clays is the Freundlich isotherm. The suitability
with Freundlich isotherm gave information that the adsorption process was dominated by
physical mechanisms (Sahan, et al., 2012).
The influence of clays addition as coagulant aid to the COD removal
The experiment was done by first determining the optimum coagulant dose (alum)
through jar test experiment. Coagulant dose variation that is added is equal to 10, 20, 30, 40,
50, and 60 mg/L of alum. Figure 10 shows the jar test results of the optimum dosage of alum.

11

Removal Efficiency (%)

40
35
30
25
20
15
10
5
0
0

20

40

60

80

100

120

Dosages of Alum (mg/L)

Figure 10. Turbidity Removal Efficiency on Dosages Variation of Alum

360

18

350

16

340

14

330

12

320

10

310

300

290

280

270

0
15

20
Dosages of Clay (mg/L)

Removal Efficiency (%)

COD (mg/L)

Figure 10 shows that the addition of alum with variation of dosages from 10 to 100
mg/L generate the removal efficiency of turbidity respectively 21%; 31.57%; 32.72%;
36.62%; 35%; 30.42%; 27.92%; 24.53%; 25.82%; and 28.38%. Based on this result, the
optimum dosage of alum is 40 mg/L, that is with the highest removal efficiency of 36.62%.
Since the hypothesis of this research is that the addition of clay are able reduce the need
for chemical coagulant (alum), then next experiment was carried out with the use of alum
dose of 1 level below its optimum dose. Alum dosage that used taken as the maximum dose
of clay addition, with variations of 15, 20, and 30 mg/L of clays dosages. Figure 11 shows
the coagulation-flocculation result with the addition of clay coagulant aid.
With the initial COD concentration of 364.26 mg/L, the addition of Arcamanik clay
with dosages 15, 20, and 30 mg/L generate the final COD concentration of 357.4; 323.02;
and 316.15 mg/L. The COD removal efficiency are 1.88%; 11.32%, and 13.2%. While for the
use of Dago clay, the final COD concentration are 350.51; 329.89; and 302.4 mg/L, with the
removal efficiency of 3.77%; 9.43%; and 16.98%.

[COD] Arcamanik Cl
[COD] Dago Cl
Eff: Arcamanik Cl
Eff: Dago Cl

30

Figure 11. COD Removal Efficiency in Coagulation Process towards Dosages Variations of
Clays
Based on that result, it can be concluded that the addition of more clays able to produce
higher COD removal efficiency, for the use of both clays. This happened because clays are
able to act as adsorbent of organic compounds, so that the organic removal efficiency of
wastewater are proportional to the dosages of clays added.

12

The next stage of research is to compare the COD removal efficiency in coagulation
process, with and without the addition of clays coagulant aid. In this experiment, dosages of
chemical coagulant that are use as comparison on coagulation-adsorption process are the
optimum coagulant dose and one level below the optimum dose (30 and 40 mg/L). The
experiment result shown on Figure 12.
COD Removal Efficiency (%)

25
20
15
10
5
0
Arcamanik Clay

Dago Clay

Alum 30 mg/L

Alum 40 mg/L

Figure 12. The Influence of Addition of Clays on Alum Coagulation

The initial concentration of COD contained in the wastewater was 409.78 mg/L. The
COD removal efficiency of processes: with addition of Arcamanik clay, Dago clay, alum
only with the dose of 30 mg/L, and alum only with 40 mg/L of dose are: 13.43%; 11.94%;
8.95%; and 17.9%.
This result shows that the addition of clays were able to improve the COD removal
efficiency in coagulation process. This happened because the combination of coagulationadsorption were able to cover each other deficiencies. Organic compounds that were removed
by the process of coagulation were compounds with high molecular weight and have a
negative charge. While the use of activated carbon more effectively to adsorp compounds
with small molecular weights and are uncharged (Shen and Chaung, 1998). However, the
result was still lower than COD removal efficiency with the use of alum on its optimum dose
(40 mg/L), that was 17.9%.

CONCLUSION
Both type of clays that used have the ability as adsorbent towards organic compounds
in wastewater. The optimum condition on the use of Arcamanik and Dago clays are at pH 7
and clays dosages of 15 and 30 mg/L. COD removal reached equilibrium point on the 120th
minutes of the contact time, for the use of both Arcamanik and Dago clays.
Isotherm model that more accurately described the adsorption process in this research
was Freundlich isotherm model. The suitability with Freundlich isotherm gave information
that the adsorption process was dominated by physical mechanisms
In general, the coagulation process with the addition of clay coagulant aid was able to
increase the removal of pollutant parameters in textile wastewater. However, this research
was not able to prove the hypothesis that the addition of clay coagulant aid was able to
decrease the need for chemical coagulant.

13

References
Al-Jlil, S. A and Alsewailem, F. D.. 2009. Lead Uptake by Natural Clay. Jurnal of Applied Sciences 9 (22):
4026-4031, 2009.
Coates, J. 2000. Interpretation of Infrared Spectra, A Practical Approach: in Encyclopedia pf Analytical
Chemistry R. A Meyers pp. 10815-10837. Chichester: John Wiley & Sons Ltd, Inc.
Errais, E., Duplay, J., Elhabiri, M., Khodja, M., Ocampo, R., Baltenweck-Guyot, R., and Darragi, F. 2012.
Anionic RR120 Dye Adsorption onto Raw Clay: Surface Properties and Adsorption Mechanism.
Colloids and Surfaces A: Physicochem. Eng, Aspects 403 (2012) 69-7B.
Fair, G. M., Geyer, J. C., and Okun, D. A. 1968. Water & Wastewater Engineering Vol. 2 Water Purification &
Wastewater Treatment and Disposal. USA: John Wiley & Sons, Inc.
Glagovich, N. 2013. Infrared Spectroscopy. http://www.chemistry.ccsu.edu/glagovich (accessed date: May 30th,
2013).
Hadiwidodo, M., Huboyo, H. S., and Indriasarimmawati. 2009. Penurunan Warna, COD, dan TSS Limbah Cair
Industri Tekstil Menggunakan Teknologi Dielectric Barrier Discharge dengan Variasi Tegangan dan
Flow Rate Oksigen. Jurnal Presipitasi Vol. 7 No. 2 September 2009.
Joseph, L., Flora, J. R. V., Park, Y., Badawy, M., Saleh, H., and Yoon, Y. 2012. Removal of Natural Organic
Matter from Potential Drinking Water Sources by Combined Coagulation and Adsorption Using
Carbon Nanomaterials. Journal of Separation and Purification Technology 95 (2012) 64-72, Elsevier.
Kannan, N and Sundaram, M. M. 2001. Kinetics and Mechanism of Removal of Methylene Blue by Adsorption
on Various Carbons a Comparative Study. Journal of Dyes and Pigments 51 (2001) 25-40.
Kogure, T., Elzea-Kogel, J., Johnston, C. T., and Bish, D. L. 2010. Stacking Disorder in a Sedimentary
Kaolinite. Journal of Clays and Clay minerals, February 2010 Vol. 58 No. 1 p. 62-71.
Komarawidjaja, W. 2007. Degradasi BOD dan COD pada Sistem Lumpur Aktif Pengolahan Limbah Cair
Tekstil. Jakarta: Jurnal Tek. Ling Vol. 8 No. 1, Januari 2007.
Liu, P and Zhang, L. 2007. Adsorption of Dyes from Aqueous Solutions or Suspensions with Clay NanoAdsorbents. Journal of Separation and Purification Technology 58 (2007) 32-39.
Mahmud. 2012. Analisis dan Karakterisasi Bahan Organik Alami (BOA) Air Gambut dan Mekanisme
Penyisihan BOA Menggunakan Tanah Lempung Gambut (TLG) Sebagai Adsorben dan Koagulan.
Bandung: Dissertation of Environmental Engineer Department of Institut Teknologi Bandung.
Maoz, A and Chefetz, B. 2010. Sorption of The Pharmaceuticals Carbamazepine and Naproxen to Dissolved
Organic Matter: Role of Structural Fractions. Journal of Water Research 44 (2010) 981-989.
Muhdarina., A. W. M and Muchtar, A. 2010. Prospektif Lempung Alam Cengar sebagai Adsorben Polutan
Anorganik di dalam Air: Kajian Kinetika Adsorpsi Kation Co (II). Reaktor, Vol. 13 No. 2, Desember
2010, page 81-88.
Mumin, M. A., M. M. R. Khan., K. F. Akhter., and M. J. Uddin. 2007. Potentiality of Open Burnt Clay as an
Adsorbent for the Removal of Congo Red from Aqueous Solution. Int. J. Environ. Sci. Tech., 4 (4): 525532.
Nilawati, D. 2013. Adsorpsi Nitrogen pada Limbah Urin Manusia dengan Menggunakan Tanah Diatomit.
Bandung: Masters Thesis of Environmental Engineer Department of Institut Teknologi Bandung.
Notodarmojo, S. 2005. Pencemaran Tanah dan Air Tanah. Bandung: Institut Teknologi Bandung Publisher.
Sahan, Y., Despramita, K.., and Sultana, Y. 2012. Penentuan Daya Jerap Bentonit dan Kesetimbangan Adsorpsi
Bentonit terhadap Ion Cu (II). Jurnal Chem. Prog. Vol. 5, No. 2. November 2012.
Schaefer, C. E. G. R., Fabris, J. D., and Ker, J. C. 2008. Minerals in The Clay Fraction of Brazilian Latosols
(Oxisols): a Review. Journal of Clay minerals, March 2008 Vol. 43 No. 1 p 137-154.
Shen, Y-H and Chaung, T-H. 1998. Removal of Dissolved Organic Carbon by Coagulation and Adsorption
from Polluted Source Water in Southern Taiwan. Journal of Environmental International, Vol. 24, No.
4. Pp. 497-503, Elsevier.
Silverstein, R. M and Webster, F. X. 1998. Spectrometric Identification of Organic Compounds, 6th Ed. USA:
John Wiley & Sons, Inc.
Skoog, D. A., Holler, F. J., and Nieman, T. A. 1984. Principles of Instrumental Analysis. Hartcourt College
Publishers.
Wicaksono, I. 2012. Penyisihan Logam Krom dari Limbah Cair Penyamakan Kulit Hasil Pengolahan Secara
Konvensional Menggunakan Electric Arc Furnace Slag (EAFS). Bandung: Masters Thesis of
Environmental Engineer Department of Institut Teknologi Bandung.

14