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Removal of methyl violet dye via adsorption using activated carbon

prepared from Randu sawdust (Ceiba pentandra)
To cite this article: Achmad Chafidz et al 2018 IOP Conf. Ser.: Earth Environ. Sci. 167 012013

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

Removal of methyl violet dye via adsorption using activated

carbon prepared from Randu sawdust (Ceiba pentandra)

Achmad Chafidz1,*, Widi Astuti2, Venitalitya Augustia1, Dinda Tri Novira2 and
Nur Rofiah2

1 Department of Chemical Engineering, Universitas Islam Indonesia, Yogyakarta

55584, Indonesia
2 Department of Chemical Engineering, Universitas Negeri Semarang, Semarang
50229, Indonesia
*E-mail: [email protected]

Abstract. In this study, randu sawdust carbon used as raw material for synthesis of activated
carbon via KOH chemical activation assisted to adsorb methyl violet dye in the water.
Activation by microwave radiation was conducted to accelerate the activation time. Randu
sawdust char/carbon and randu sawdust activated carbon were characterized by FTIR, SEM,
and BET. The results showed that the randu sawdust carbon and the activated carbon have a
functional group which can adsorb methyl violet. Randu sawdust activated carbon has a larger
pore and surface area than the randu sawdust carbon/char. The optimum adsorption occured at
pH 9 and 90 minute of contact time. The maximum adsorption capacity of methyl violet dye by
the randu sawdust activated carbon was approximately 531.16 mg g-1.

1. Introduction
Dye production in the world is estimated at 7 x 105 to 106 tons per years, and approximately 15% of
the dye wastes have been discharged to the environment [1]. One type of dyes that is most commonly
found is methyl violet, which generally comes from industrial inks, paints and textiles [2]. The
existence of this dye is dangerous for aquatic life because it is considered as mutagenic and mitotic
poison, and thus carcinogenic. Various methods have been developed to overcome the pollution of this
dye in the waters, including photocatalytic [3], membrane [4], and adsorption [5]. Adsorption is a
promising alternative method that relatively simple, inexpensive, and can be applied at low
concentrations. Several types of adsorbents have been used to reduce dye concentration in the waters.
Activated carbon-MnOx hydrothermally from coconut shell is able to adsorb azo dye at 99.1% [6].
However, this process requires a relatively high energy, and therefore the active carbon is expensive
and difficult to be applied in the industry. Therefore, the synthesis of activated carbon which is simple
and inexpensive is needed. One of the example is the synthesis of activated carbon assisted by
microwave radiation as heating system and with KOH as the activator.
Microwave is an electromagnetic wave that gives a heat effect when the wave is absorbed on the body
object. Microwave radiation offers several advantages over conventional heating methods, including
rapid temperature rise, a uniform temperature distribution, and reduction of processing time, as well as
the energy consumption [7]. In this study, the synthesis of activated carbon using randu sawdust as a
raw material has been investigated. Randu is widely available on the Java Island, but it has limited use
and it has a low of economic value because it is generally used for casting of concrete for the building,
but then go into the waste. Therefore, the potentials of this randu to be used as a raw material for the
synthesis of an activated carbon have been investigated. Randu as an adsorbent has an ability to give

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

the adsorption percentage over 90% [8], [9]. In the current study, synthesis of activated carbon
prepared from randu sawdust was investigated. The prepared char/carbon and activated carbon were
characterized for surface area and pore size distribution, Fourier Transform Infra-Red (FTIR)
spectroscopy, and Scanning Electron Microscopy (SEM). The adsorption capacity of activated carbon
was evaluated using methyl violet dye as the adsorbate. The effect of operating parameters, such as pH,
contact time, initial methyl violet concentration were investigated.

2. Materials and methods

2.1. Adsorbate
Methyl violet (chemical grade reagent) was used as the adsorbate without further purification. The
sample solution is prepared by dissolving methyl violet powder into distilled water at different initial
concentrations (50, 100, 150, 200, 250, 300, 350, 400, 450, and 500 mg/L). The chemical structure of
methyl violet shown in Figure 1.

Figure 1. Chemical structure of methyl violet

2.2. Carbonization of Randu wood dust

Randu sawdust used as a raw material in this study was obtained from the local sawmill. To prepare
the activated carbon, the randu sawdust was washed and then dried in the oven at 105°C to remove the
moisture. The dried randu sawdust was then crushed and sieved using a 150 mesh sieve. Afterward,
carbonization of the randu sawdust was achieved by heating it in a furnace at temperature of 700°C
for 2 hours.

2.3. Microwave-induced Activation Process

The prepared char/carbon was mixed with potassium hydroxide (KOH) with an impregnation ratio of
1:1 (wt/wt%). The resulted char slurry was then placed in a glass reactor installed in the microwave
chamber. The microwave was operated with an input power of 180 W and frequency of 2.45 GHz. The
heating time was set at 10 min. Pure nitrogen flow was maintained at a flow rate of 1 cm3 min-1 during
the activation and cooling processes. The resulted activated carbon was washed with 0.1 M HCl and
then rinsed with distilled water until pH of 6-7 was attained and finally dried in an oven at 120°C. The
dried activated carbon is ready to use for the adsorption tests.

2.4. Characterization of char and activated carbon

The surface area of the char and activated carbon was determined using the Brunauer-Emmet-Teller
(BET) method. Whereas, the average width of the pores and pore size distribution was determined
using the Barrett-Joyner-Halenda (BJH). The surface functional groups were characterized by Fourier
Transform Infra-Red (FTIR) spectroscopy in the scanning range of 4000-400 cm-1. The surface
morphology of char and activated carbon was characterized using a Scanning Electron Microscopy
(SEM).

2.5. Adsorption experiments

Several batch adsorption experiments were conducted in 250 mL Erlenmeyer flasks containing 0.06 g
of activated carbon and 100 mL of methyl violet solution and placed in a shaker at 120 rpm. The effect
of pH in the range of 3, 5, 7, and 9 was studied. The pH was adjusted using 0.1 M HCl and 0.1 M

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

NaOH. The effect of contact times (5, 10, 15, 20, 30, 60, 90, 120, 150, and 180 min) was also carried
out to study the equilibrium adsorption time. Methyl violet with different initial concentrations (50,
100, 150, 200, 250, 300, 350, 400, 450, and 500 mg/L) were also studied. The concentrations of
methyl violet before and after the adsorption were analyzed via absorbance measurement using a UV-
Vis Spectrofotometer at 581 nm. The methyl violet adsorbed at equilibrium qe (mg/g), was calculated
using Eq. (1):
C  Ce 
qe  o V (1)
M
where Co (mg/l) and Ce (mg/l) are the initial and equilibrium concentrations of methyl violet,
respectively, V (L) is the volume of solution and M (g) is the dry mass of randu sawdust activated
carbon [10].

3. Results and discussion

3.1. Characterization results of char and activated carbon

The FTIR analysis was conducted to confirm the presence of functional groups in the char and
activated carbon of randu sawdust are capable to adsorb the methyl violet. The FTIR spectrum are
shown in Figure 2.

Figure 2. FTIR spectrum of char and activated carbon

The results of the randu carbon FTIR spectra showed broad absorption peak at 3431.32 cm-1 indicating
the presence of O-H group, which were derived from the alcohol compounds. Absorption peaks at
1435.12 cm-1 indicating the presence of aromatic C=C groups. Whereas, the presence of group C-O-H
was indicated by absorption peak at 877.15 cm-1. There was also a decrease in absorption peaks at
wavenumber of 3431.32 cm-1 and 1435.12 cm-1. The reduced intensity of absorption peaks at wave
number of 1435.12 cm-1 that belongs to C=C group was probably caused by a reaction between some
Carbon with the KOH. Whereas, the reduced OH group at wave number of 3431.32 cm-1 was likely
caused by the partial OH group, which reacted with KOH. While, the widening of the peak at about
wave number of 1500 cm-1 was probably caused by the group C-O formation of aldehyde numbers
waves almost coincide with the C=C. Additionally, Scanning Electron Microscopy images of the char
and activated carbon at 5000 X magnification are shown in Figure 3.

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

Figure 3. SEM micrographs of a) char and b) activated carbon

As seen in Figure 3a, the char seemed to have a lot of impurities product of carbonization. While the
activated carbon was more pure, which is likely due to the N2 flowing during the activation process
(see Figure 3b). Additionally, the BET analysis shows that the randu sawdust activated carbon has a
larger of specific surface area, i.e. 69.486 m2/g. The pore size distribution of the activated was
analyzed using the method of Barret Joyner Halenda (BJH), and was found to be approx. 17.230 nm.
Whereas, the randu char/carbon has a specific surface area of 5.587 m2/g with a pore size distribution
approx. 17.185 nm.

3.2. Adsorption of methyl violet

Effect of pH on the adsorption of methyl violet studied at various pH 3, 5, 7, and 9 is shown in Figure
4. The figure shows that at pH 9 dye adsorbed amount reached the highest rate (99.76%). Randu
sawdust activated carbon inclined protonated at low pH so that the active sites to be positively
contents. This causes the repulsion between the active sites with methyl violet that was also positively
contents, and hence the adsorption process is difficult to occur. It can be concluded that the optimum
pH of methyl violet adsorption by randu sawdust activated carbon is at pH = 9.
The effect of contact time on the adsorbed of methyl violet by randu sawdust activated carbon at
initial concentration of 100 mg/L is shown in Figure 5. Both the curves showed that the adsorption
increased rapidly in the first 10 min, and thereafter gradually slowed down until it reached the
equilibrium time. This phenomena was likely due to a large number of vacant surface sites were
available for adsorption during the initial stage, and hence the tendency of methyl violet adsorbed by
activated carbon was still high. Once the equilibrium was attained, the amount of methyl violet
adsorbed did not change with the further increase of time.

Figure 4. Effect of pH on the adsorbed of methyl violet

(condition: initial concentration = 100 mg L-1, contact time =
120 min, activated carbon dose = 0.6 g L-1)

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

Figure 5. Effect of contact time on the adsorbed of methyl violet

(condition: initial concentration = 100 mg L-1, pH = 9, activated
carbon dose = 0.6 g L-1)

Figure 6 shows that the amount of methyl violet adsorbed increased with the increase of methyl violet
initial concentration and remained constant after reached the equilibrium. This was likely due to the
fact that increasing concentration will also increase the driving force, so the rate of mass transfer of
adsorbate onto the activated carbon will also be faster [11].

Figure 6. Effect of initial concentration on the adsorbed of methyl

violet (condition: pH = 9, contact time = 90 min, activated carbon dose
= 0.6 g L-1)

4. Conclusion
The current study has demonstrated the suitability of randu sawdust for the preparation of activated
carbon by microwave heating-induced KOH activation. The high surface area activated carbon was
produced in a short activation time by the microwave heating system. The optimum adsorption of the

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8th International Conference on Environment Science and Engineering (ICESE 2018) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 167 (2018)
1234567890 ‘’“” 012013 doi:10.1088/1755-1315/167/1/012013

methyl violet was occured at pH 9 and the equilibrium time of 90 minute. The maximum adsorption
capacity of methyl violet dye by randu sawdust activated carbon was approximately 531.16 mg g-1.

5. References
[1] Gupta V K and Suhas 2009 Aplication of Low-cost Adsorbent for Dye Removal – A Review
Journal Enviromental Management 90: 2313-2342.
[2] Christina M, S Mu’nisanatun, Saptaji R, Marjanto D 2007 Studi Pendahuluan Mengenai
Degradasi Zat Warna Azo (Metil Orange) dalam Pelarut Air Menggunakan Mesin Berkas
Elektron 350 kev/10 ma Jurnal Forum Nuklir Vol. 1 No. 1.
[3] Zhang Y, Sun X, Yang G, Zhu Y, Si H, Zhang J, and Li Y 2016 Preparation and
Characterization of Bifunctional BiOClxIy Solid Solutions with Excellent Adsorption and
Photocatalytic Abilities for Removal of Organic Dyes Materials Science in Semiconductor
Processing 41: 193-199.
[4] Shi J, Wu T, Teng K, Wang W, Shan M, Xu Z, Lv H, and Deng H 2016 Simultaneous
Electrospinning and Spraying Toward Brach-Like Nanofibrous Membrans Functionalised with
Carboxylated MWCNTs for Dye Removal Materials Letters 166: 26-29.
[5] Fontana K B, Chaves E S, Sanchez J D S, Watanabe E R L R, Pietrobelli J M T A, and Lenzi G
G 2016 Textile Dye Removal from Aqueous Solution by Malt Bagasse: Isotherm, Kinetic and
Thermodynamic Studies Ecotoxicology and Evironmental Safety 124: 329-336.
[6] Xu L, Li X, Ma J, Wen Y, and Liu W 2014 Nano-MnOx on Activated Carbon Prepared by
Hydrothermal Process from Fast and Highly Efficient Degradation of Azo Dyes Applied
Catalysis A: General 485: 91-98.
[7] Yuen F K and Hameed B H 2009 Recent Developments in the Preparation and Regeneration of
Activated Carbon by Microwaves Advances Colloid Interface Science 149: 19-27.
[8] Astuti W, Sulistyaningsih T, and Maksiola M 2016 Chemical Modified Kapok Sawdust as
Adsorbent of Methyl Violet Dye from Aqueous Solution Jurnal Teknologi 78(9): 35-42.
[9] Maziyyah D F 2015 Modifikasi Adsorben Berbasis Kayu Randu dengan Metode Pemanasan
dan Aplikasinya sebagai Penjerap Zat Warna Methyl Violet pada Limbah Industri Batik Tugas
Akhir Jurusan Teknik Kimia Universitas Negeri Semarang.
[10] Njoku V O, Foo K Y, Asif M, and Hameed B H 2014 Preparation of Activated Carbon from
Rambutan (Nephelium lappaceum) peel by Microwave-induced KOH Activation for Acid
Yellow 17 Dye Adsorption Chemical Engineering Journal 250: 198-204.
[11] Zou W, Bai H, Gao S, Li K 2013 Characterization of modified sawdust, kinetic and equilibrium
studyabout methylene blue adsorption in batch mode. Korean Journal of Chemical Engineering
30 (1): 111-122.