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Article
Adsorptive Removal of Methyl Orange and Methylene Blue from
Aqueous Solution with Finger Citron Residue-Based Activated Carbon
Rui Gong, Jingjing Ye, Wei Dai, Xiaoyang Yan, Jue Hu, Xin Hu, Shuang Li, and He Huang
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie402138w • Publication Date (Web): 11 Sep 2013
Downloaded from http://pubs.acs.org on September 17, 2013

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Page 1 of 27 Industrial & Engineering Chemistry Research

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4 Adsorptive Removal of Methyl Orange and Methylene Blue
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6 from Aqueous Solution with Finger Citron Residue-Based
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9 Activated Carbon
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11 Rui Gong,† Jingjing Ye,† Wei Dai,*,† Xiaoyang Yan,† Jue Hu,† Xin Hu,† Shuang
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14 Li,‡ and He Huang,*,‡
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16 †College of Chemistry and Life Science, Zhejiang Normal University, Zhejiang Province Jinhua
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19 321004, People’s Republic of China
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21 ‡College of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology,
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24 Nanjing 210009, People’s Republic of China
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26 ABSTRACT: Activated carbon derived from finger citron residue (FAC) was tested as
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29 a new type of adsorbents to remove the harmful dyes (anionic dye methyl orange (MO)
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31 and cationic dye methylene blue (MB)) from contaminated water. Liquid phase
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34 adsorption experiments were conducted and the maximum adsorptive capacity was
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36 determined. Various conditions were evaluated, including initial dye concentration,
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39 adsorbent dosage, contact time, solution pH, and temperature. The Langmuir and
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Freundlich adsorption models were used to describe the equilibrium isotherm and
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44 isotherm constant calculation. It was found that the adsorption capacity of FAC is
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much higher than those of the other types of activated carbons. Maximum equilibrium
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49 adsorption capacities of 934.58 mg/g and 581.40 mg/g for MO and MB were achieved.
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Three simplified kinetic models including pseudo-first-order, pseudo-second-order
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54 and intra-particle diffusion equations were used to investigate the adsorption process.
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The pseudo-second-order equation was followed for adsorption of MO and MB on
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4 FAC. Temperature-dependent adsorption behaviors of MO and MB show that the
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6 adsorption is a spontaneous and endothermic process accompanying an entropy
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9 increases (the driving force of the adsorption). This work indicates that FAC could be
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11 employed as a low cost alternative to commercially available activated carbon in the
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14 removal of dyes from wastewater.
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16 1. INTRODUCTION
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19 Removing dyes from wastewater before its discharge is a necessary practice for water
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21 industry. The significant increase in the use of dyes by various industries is causing
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24 severe damage to the environment due to incapability of bio-degradability and high
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26 toxicity of these compounds.1 It is difficult to degrade dye materials because they are
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29 very stable against light and oxidation reactions.2 In the process of removal of dye
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31 materials from contaminated water, several methods such as physical, chemical and
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34 biological ones have been investigated.3,4 Among them, removal of dyes by physical
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36 adsorption technologies is regarded as one of the competitive methods because of
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39 high efficiency, economic feasibility and simplicity in design/operation.5 Thus,
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adsorbents with a high capacity play a vital role in the performance of adsorption
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44 treatment of dyes. Various commonly used adsorbents that provide significant
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removal of dyes have been discussed.5,6 In fact, adsorption using activated carbons
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49 has been shown to be one of the most efficient procedures in the elimination of dye
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compounds from wastewater and air. Additionally, the other applications of activated
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54 carbon in the market are also vast, for example, serving as catalysts and catalyst
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supports. However, commercially available activated carbons are mostly derived from
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4 different precursors including wood,7 peat,8 nutshells,9,10 or coal,11 which are still
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6 considered relatively expensive.12,13 The wide usage of activated carbon is now
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9 creating the immediate need for development of low-cost procedures. Low-cost
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11 activated carbons prepared from the other agricultural byproducts and waste materials
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14 have been investigated for a long time. Finger citron (Figure 1), a subtropical plant,
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16 grows widely in Fujian, Zhejiang, Guangdong and Sichuan provinces of China.14
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19 Finger citron beverage is a favorite health food,15 but a lot of finger citron residues are
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21 produced during the production process. As waste materials, the finger citron residues
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24 have to be disposed as garbage, which can also sometimes cause another environment
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26 problem. In our previously work,16 finger citron-based activated carbons (FAC) were
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29 successfully prepared from finger citron residues. Due to their highly micro-porosity
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31 and surface area,17 FACs are promising materials for adsorptive removal of dyes.
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34 On the other hand, methyl orange (MO) is one of the well-known acidic/anionic
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36 dyes, and has been widely used in textile, printing, paper, food and pharmaceutical
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39 industries and research laboratories.18 Additionally, methylene blue (MB) is one of the
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most common cationic dying materials for wood, silk and cotton.19 The structure of
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44 MO and MB are shown in Scheme 1. Though MO and MB are not highly hazardous,
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it can cause some harmful effects. Acute exposure to MO or MB can cause increased
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49 heart rate, vomiting, shock, cyanosis, jaundice, quadriplegia, and tissue necrosis in
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humans.20 Thus, removal of MO and MB from wastewater and/or process effluent is
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54 very important due to their potential toxicity to human and environment. MO and MB
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for the reasons stated above were selected in this study as the model dyes.
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4 The main objective of the present work is to report adsorption of an anionic dye
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6 (MO) and a cationic dye (MB) over FAC because the removal of both cationic and
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9 anionic dyes are not readily achieved simultaneously21 and the adsorption can be
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11 understood much by a comparison between the two adsorbates. The other
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14 commercially available activated carbons including CS-AC (Coconut Shell-Based
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16 Activated Carbon), C-AC (Coal-Based Activated Carbon), NS-AC (Nut Shell Based
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19 Activated Carbon), and W-AC (Wood Based Activated Carbon) were also studied in
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21 this work as controls. Adsorptive equilibrium isotherms, kinetics, and
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24 thermodynamics were processed to understand the adsorption mechanism of the dyes
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26 molecules onto the FAC.
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29 2. EXPERIMENTAL
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31 2.1. Materials. An aqueous stock solution of MO and MB was prepared by
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34 dissolving MO (C14H14 N3NaO3S, MW: 327.34, Sigma-Aldrich) and MB
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36 (C16H18ClN3S, MW: 373.9, Sigma-Aldrich) in deionized water. The CS-AC, C-AC,
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39 NS-AC and W-AC activated carbons were provided by Guangfu Refine Chemicals,
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Tianjin of China. The activated carbons were washed and sieved into the desired
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44 particle size before coming in contact with dye aqueous solution. All the other
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reagents were of analytical reagent grade.
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49 2.2. Preparation of FAC. FAC from finger citron residues was prepared by a
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patented KOH activation procedure17 that was previously proposed by our group. In a
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54 typical preparation, 2 g of precursor in the particle size 150 µm was mixed with 10 g
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of KOH powder. Hence, the mass ratio of KOH and finger citron residues precursor
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4 was 5:1 and the resulting mixture was placed into a horizontal pipe reactor (50 mm
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6 o.d.) for activating as follows. (i) Nitrogen gas was allowed to flow through the
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9 reactor at a rate of 40 mL/min and maintained at this flow rate throughout the whole
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11 activation process. (ii) The temperature of the reactor was raised to the activation
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14 temperature (1123 K) at a heating rate of 1 K/min. (iii) The reactor was held at the
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16 activation temperature for 40 min. (iv) Finally, it was cooled down to room
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19 temperature. The samples thus obtained were washed with distilled water until the
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21 filtrate appeared neutral. The final product (FAC) was obtained by heating these
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24 samples at 423 K under vacuum for 24 h.
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26 2.3. Nitrogen adsorption. Specific surface areas and pore volumes were
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29 determined by N2 adsorption. An automated adsorption apparatus (Micromeritics,
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31 ASAP2020) was used for these measurements. N2 adsorption was carried out at liquid
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34 N2 temperature (77 K). The specific surface areas were calculated using the BET
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36 equation by assuming a section area of nitrogen molecule to be 0.162 nm2. The t-plot
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39 method was applied to calculate the micropore volumes and surface areas. The total
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pore volume was estimated to be the liquid N2 volume at a relative pressure of 0.99.
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44 The pore size distribution was calculated by density functional theory (DFT).
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2.4. Batch equilibrium studies. The equilibrium isotherms of MO (99.8 %,
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49 Sigma-Aldrich) and MB (99.8 %, Sigma-Aldrich) adsorption on FAC were
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determined by performing adsorption tests in 100 mL erlenmeyer flasks where 50 mL
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54 of MO and MB solutions with different initial concentrations (50-500 mg/L) were
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placed in each flask. The pH value of the solutions was gradually adjusted to 7 by
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4 adding small amount of 0.1 M HCl solution. 0.02 g of each of the prepared FAC, with
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6 particle size of 150 µm, were added to each flask and kept in a shaker with 150 rpm at
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9 different temperatures (303-323 K) for 4 h to reach equilibrium. Then the samples
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11 were filtered and the residual concentrations of MO and MB in the filtrate were
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14 analyzed by a UV-Visible spectrophotometer (Shimadzu UV-160A) at maximum
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16 wave lengths of 464 nm and 664 nm, respectively. It was found that the calibration
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19 curve was very reproducible and linear over the concentration range used in this work.
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21 The adsorbed amount of MO and MB at equilibrium, qe (mg/g) was calculated by the
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24 following expression:
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26 (Co − Ce ) ⋅ V
qe = (1)
27 W
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29 where Co and Ce (mg/L) are the initial and equilibrium concentrations of MO or MB
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31 solution, respectively; V (L) is the volume of solution, and W (g) is the weight of FAC
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34 used.
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36 The linear form of Langmuir′s isotherm model22 is given by the following equation:
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39 Ce 1 1
= + ( ) ⋅ Ce (2)
40 qe qL ⋅ K L qL
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43 where qL (mg/g) is the Langmuir maximum uptake of MO and MB per unit mass
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45 adsorbent, KL (L/mg) is the Langmuir constant related to the rate of adsorption.
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48 The well-known logarithmic form of Freundlich model23 is given by the following
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50 equation:
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52 1
53 ln qe = ln K f + ( ) ⋅ ln Ce (3)
n
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55 where Kf and n are Freundlich constants, with n indicating the favorableness of the
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58 adsorption process and Kf the adsorption capacity of the adsorbent. Kf can be defined
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4 as the adsorption or distribution coefficient and its represents the quantity of dye
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6 adsorbed onto activated carbon adsorbent for a unit equilibrium concentration. The
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9 slope 1/n ranging between 0 and 1, is a measure of adsorption intensity or surface
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11 heterogeneity, becoming more heterogeneous as its value gets closer to zero.
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14 2.5. Adsorption kinetics. The procedure used for kinetic tests was identical to
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16 that used for equilibrium experiments. The aqueous samples were taken at the desired
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19 time intervals, and the concentrations of MO and MB were similarly measured. The
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21 adsorbed amount of MO and MB at time t, qt (mg/g), was calculated by:
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23 (Co − Ct ) ⋅ V
24 qt = (4)
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W
26 where Ct (mg/L) is the liquid-phase concentration of MB and MO solution at time t
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29 (min). Pseudo-first order model,24 pseudo-second order model,25 and intra-particle
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31 diffusion model26 were used to analyze the kinetic data. These models can be
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34 expressed as:
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36 Pseudo-first order model: ln(qe − qt ) = ln(qe ) − K1t (5)
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39 t 1 t
Pseudo-second order model: = + (6)
40 qt K 2 qe qe
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43 Intra-particle diffusion model: qt = K 3t 1/ 2 (7)
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45 where qe and qt (mg/g) are the uptake of MO and MB at equilibrium and at time t
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48 (min), respectively, K1 (1/min) is the adsorption rate constant, K2 (g/mg.min) is the
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50 rate constant of second-order equation, K3 (mg/g.min1/2) is the intra-particle diffusion
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53 rate constant.
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55 In order to quantitatively compare the applicability of different kinetic models in
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58 fitting to data, a normalized standard deviation, △q (%), was calculated as below:
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(qe, exp − qe, cal )
4 ∆q(%) = × 100% (8)
5 qe, exp
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2.6. Adsorption thermodynamics. Thermodynamic behavior of MO and MB
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10 adsorption onto FAC was evaluated by the thermodynamic parameters including the
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changes in free energy (G), enthalpy (H), and entropy (S). These parameters are
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15 calculated from the following equations:
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17 ∆S ∆H
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ln( K d ) = − (6)
R RT
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20 ∆G = − RT ln( K d ) (7)
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22
qe (W / V )
23 Kd = (8)
24 Ce
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26 where R is the universal gas constant 8.314 (J/mol K), T is the temperature (K), and
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29 Kd is the distribution coefficient for the adsorption.
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31 3. RESULTS AND DISCUSSION
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34 3.1. Material characterization. The nitrogen adsorption isotherms and the pore
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36 size distribution curves of FAC, W-AC, CS-AC, C-AC and NS-AC at 77 K are shown
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39 in Figure 2 and Figure 3, respectively. Clearly, all these samples show type I
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adsorption isotherms according to the IUPAC classification.17 The properties of the
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44 adsorbents are collected in Table SI.1. The BET surface area and pore volume of FAC
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sample were 2887 m2/g and 1.60 cm3/g, respectively, while those of the other
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49 activated carbons are not more than 2023 m2/g and 1.54 cm3/g, respectively. The pore
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size distributions calculated by density functional theory (DFT) prove that the pore
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54 size of these activated carbons range from 1 to 5 nm. The huge surface area of the
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FAC is much higher than the other activated carbons, which provides the huge
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4 capacity for dye molecules’ adsorption inside the pore structure.
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6 3.2. Effect of pH. It is known that the solution pH can affect the surface charge of
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9 the adsorbent, the degree of ionization of dyes, as well as the structure of the dye
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11 molecules. So the solution pH is an important parameter during the dye adsorption
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14 process. Effect of pH on adsorption was studied using 450 mg/L dye concentration
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16 and at 318 K. The results are given in Figure 4. The uptake capacities of dyes were
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19 significantly changed over the pH range of 2-7. The adsorption capacities of the dyes
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21 were constant at pH 7-10. The lowest quantities of the MO and MB adsorption
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24 recorded at pH 2 were 770.43 and 431.54 mg/g, respectively. The equilibrium
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26 adsorption (qe) was found to increase with increasing pH. A similar behavior was
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29 reported in the literatures.18,19,27 The adsorption mechanism has been discussed in
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31 section 3.7 for details.
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34 3.3. Effect of adsorbent dosage. Under the conditions of pH 7, Co of 450
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36 mg/L, and contact time of 4 h, the effects of amount of FAC on adsorption of MB and
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39 MO dyes are shown in Figure 5. The results show that the adsorption capacities of
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MO and MB in the first stage increase rapidly with the increase in the adsorbent dose,
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44 and then the adsorption capacities are not changed significantly with the further
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increase in the adsorbent dose. It can be seen that the adsorption capacities of the dyes
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49 reach adsorption saturation with the adsorbent dose more than 0.4 g/L. Thus, 0.4 g/L
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was chosen as the optimum dose and used in the further experiments. The
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54 two-stage-dependent adsorption behavior was also reported in the literature.19
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3.4. Adsorption isotherms. The adsorption isotherm indicates how the
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2
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4 adsorption molecules distribute between the liquid phase and the solid phase when the
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6 adsorption process reaches an equilibrium state. The analysis of the isotherm data by
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9 fitting them to different isotherm models is an important step to find the most suitable
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11 model that can be used to describe adsorption process.28 The Langmuir and
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14 Freundlich isotherms selected here are widely used to describe the dye adsorption at
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16 the solid-liquid interface. The adsorption isotherms of MB and MO at 318 K and pH 7
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19 on the five selected activated carbons at a solid/liquid ratio of 0.4 g/L are presented in
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21 Figure 6 and Figure 7, respectively. The obtained experimental equilibrium adsorption
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24 data are then fitted using Langmuir and Freundlich isotherm models by Eq.(2) and
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26 Eq.(3). The calculated constants according to the two isotherm equations along with
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29 R2 values (standard deviation) are presented in Table SI.2. This table shows that the
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31 Langmuir isotherm gives the best fittings with R2＞0.998. The good fittings to the
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34 Langmuir model for the dyes also suggest that the adsorption is limited with a
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36 monolayer coverage and the surface is relatively homogeneous. On the other hand, for
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39 MB and MO dyes, the maximum monolayer adsorption capacity (qL) is significantly
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higher on FAC and varies in the order of FAC＞W-AC＞CS-AC＞C-AC＞NS-AC.
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44 Thus, it is predicted the dyes’ uptake capacity of activated carbons is significantly
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higher with the increased surface area. Moreover, for FAC, the uptake capacity of MO
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49 is also significantly higher than that of the MB (approximately 1.6-fold higher). This
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may be due to the different molecule sizes and function groups of the two dyes. The
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54 larger dye molecule is difficult to penetrate into the adsorbent mesoporous structure
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due to the pore blockage.29 The adsorption capacities of MB and MO on FAC in this
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4 work are summarized in Table SI.3, together with those of the control adsorbents. It is
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6 clear that the adsorption capacity of FAC is superior to the other previously reported
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9 adsorbents.29–32
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11 3.5. Adsorption kinetics. The effect of contact time on adsorption capacity of
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14 FAC to MB oand MO at different temperature is shown in Figure 8 and Figure 9,
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16 respectively. These figures show that the adsorption capacity for MB and MO
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19 increases with the increase of contact time, and the adsorption reaches equilibrium
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21 within about 1 h. The saturation capacities of 863 mg/g, 887 mg/g, 916 mg/g, 935
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24 mg/g and 695 mg/g at 303 K, 308 K, 313 K, 318 K and 323 K are obtained at 4 h
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26 contact time, 450 mg/L initial concentration, 7 pH value and 0.4 g/L adsorbent dose.
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29 These figures also show that rapid increase in capacity for the dyes is achieved during
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31 the first 0.3 h. The fast adsorption at the initial stage may be due to the availability of
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34 the uncovered surface area and the remaining active sites on the adsorbent.
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36 The experimental kinetic data of MB and MO, calculated from Eqs. (5), (6) and (7),
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39 were correlated by three kinetic models: pseudo-first order, pseudo-second order and
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41
intra-particle diffusion models. The calculated constants of the three kinetic equations
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44 along with R2 values at different temperatures are presented in Table SI.4. As seen in
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Table SI.4, there is a large difference between the experimental and calculated
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49 adsorption capacity values when the pseudo-first model was applied. However, high
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R2 values (0.9999) are obtained with the linear plot of t/qt versus t, suggesting the
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54 pseudo-second order adsorption kinetics. Additionally, the pseudo-second order
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kinetic model predicts a good agreement between the experimental and calculated
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4 adsorption capacity values ∆q (%). According to intra-particle diffusion model, a plot
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6 of the amount of dye adsorbed (qt) versus the square root of time (t1/2) should be linear,
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9 and if these lines pass through the origin, then the intra-particle diffusion is the only
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11 rate-controlling step.33 However, as shown in Figure 10, the plots are not linear over
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14 the whole time range and, instead, can be separated into multi-linear curves,
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16 illustrating that multiple stages were involved in the adsorption process. The results
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19 indicated that the adsorption of MO and MB dyes onto FAC involved more than one
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21 process, and the intra-particle transport is not the rate-limiting step. Such finding is
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24 similar to that made in previous works on adsorption.34–36
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26 3.6. Adsorption thermodynamics. On the basis of the MB and MO adsorption
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29 isotherm data which were calculated from Eq. (1), the value of Kd was calculated from
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31 Eq. (8) at each temperature.37 Then, according to Eqs. (6) and (7), the ∆H and ∆S
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34 parameters for MB and MO adsorption can be derived from the slope and intercepts
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36 of the plot of In(Kd) versus 1/T (Figure 11). The calculated values of ∆H, ∆S, and ∆G
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39 are listed in Table SI.5.
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41
The obtained values for Gibbs free energy change (∆G) are -28.19 and -18.63,
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44 -29.16 and -19.14, -30.24 and -19.38, -31.09 and -19.57, -30.66 and -19.78 kJ/mole
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for MO and MB adsorption on FAC at 303, 308, 313, 318 and 323 K, respectively.
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49 The negative ∆G values indicate thermodynamically spontaneous nature of the
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51
adsorption. The decrease in ∆G values with increasing temperature shows a decrease
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54 in feasibility of adsorption at higher temperatures. The ∆H parameters are 3.11 and
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6.14 kJ/mole for MO and MB adsorption on FAC, respectively. The positive ∆H is an
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4 indicator of endothermic nature of the adsorption and its magnitude also gives
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6 information on the type of adsorption, which can be either physical or chemical.
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9 Usually, the adsorption enthalpy ranging from 2.1 to 20.9 kJ/mol corresponds to a
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11 physical adsorption.38 Physical adsorption occurs when the intermolecular attractive
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14 forces between the molecules of adsorbate and adsorbent are greater than those
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16 between the adsorbate themselves. Physical adsorption, which may be a
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19 monomolecular or multi-molecular layer, occurs rapidly. In contrast, chemisorption
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21 involves the formation of chemical bonds between the adsorbate and adsorbent. It
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24 takes place only at high temperatures and may be slow.38 In this study, the adsorption
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26 heat of MO and MB is in the range of physical adsorption. The ∆S values are 195.41
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29 and 42.27 J/mole for MO and MB adsorption on FAC, respectively. The positive ∆S
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31 value suggests an increase in the randomness at adsorbent-solution interface during
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33
34 the adsorption process.
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36 3.7. Adsorption mechanism. The surface structure of activated carbons has a
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38
39 strong influence on their adsorptive selectivity and capacity. The mechanism of dyes
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41
adsorption is controlled by various factors like physical and/or chemical properties of
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43
44 activated carbons, mass transfer process, etc.39,40 MO and MB are ideally planar
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46
molecule and therefore can easily adsorb on FAC by π-π stacking interaction between
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49 the aromatic backbone of the dye and hexagonal skeleton of FAC.27,30,41 For example,
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52
the MO molecule presents in solution in the state of quinone and azo structures (pKa =
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54 3.47, Scheme 2), depending on the solution pH.42 It is predicted that the azo structure
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should have a more conjugated π system30 than the quinone counterpart. Indeed, the
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4 adsorption capacity of MO at basic condition was higher than that at acidic condition
5
6 (Figure 4), predicting the role of π-π stacking interactions on dye adsorption on FAC.
7
8
9 However, the other interaction forces other than π-π stacking interaction could also
10
11 contribute to the adsorption process. For example, it has been proved that the
12
13
14 electrostatic force is also involved in adsorption of positively charged MB on
15
16 negatively charged surfaces of activated carbons.18,19 Thus, the electrostatic attraction
17
18
19 between FAC and MB could be partially responsible for the adsorption.
20
21 4. CONCLUSION
22
23
24 Adsorption ability of the FAC is evaluated by choosing the methylene blue (MB) and
25
26 methyl orange (MO) as model adsorbates. Batch adsorption tests demonstrate that the
27
28
29 adsorption is affected by various conditions such as contact time, solution pH and
30
31 initial dye concentration. Adsorption kinetics follows the pseudo-second-order model.
32
33
34 Equilibrium data are fitted by Langmuir and Freundlich isotherms and the equilibrium
35
36 data are better described by Langmuir isotherm model, with maximum equilibrium
37
38
39 adsorption capacity of 934.58 mg/g (MB) and 581.40 mg/g (MO), respectively. The
40
41
π-π stacking interactions between the surface of activated carbon and dyes account for
42
43
44 the high adsorptive performance of the FAC. Since the finger citron residues are
45
46
agricultural byproducts and actually waste materials, besides resolving the finger
47
48
49 citron residues’ environmental issue, the usage of finger citron residues as raw
50
51
materials for activated carbon provide a way to produce a promising low-cost
52
53
54 adsorbent for removal of dyes from aqueous solution.
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AUTHOR INFORMATION
5
6 Corresponding Author
7
8
9 *,† E-mail: daiwei@zjun.edu.cn. Fax: +86-579-82282531. Tel:+86-579-82282269.
10
11 *,‡ E-mail: huangh@njut.edu.cn. Fax: +86-25-83172094. Tel: +86-25-83172101.
12
13
14 Notes
15
16 The authors declare no competing financial interest.
17
18
19
ACKNOWLEDGMENT
20
21 This work was supported by the Public Projects of Zhejiang Province of China (No.
22
23
24 2013C31094), Zhejiang Qianjiang Talent Project (No. QJD1302014) and
25
26 the Educational Commission of Zhejiang Province of China (No. Y201329292).
27
28
29
ASSOCIATED CONTENT
30
31 Supporting Information
32
33
34 Structural properties of activated carbons (Table SI.1.), constants and correlation
35
36 coefficients of Langmuir and Freundlich models (Table SI.2.), comparison of the
37
38
39 maximum monolayer uptake capacities of MB and MO dyes on various adsorbents
40
41
(Table SI.3.), kinetic parameters for MO and MB adsorption on FAC (Table SI.4.),
42
43
44 and the thermodynamics adsorption parameters for MB and MO on FAC (Table SI.5.).
45
46
This material is available free of charge via the Internet at http://pubs.acs.org.
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48
49
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4 Scheme captions:
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6 Scheme 1. Chemical Structures of MO (a) and MB (b).
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9 Scheme 2. The Structure of Methyl Orange Under Acidic or Alkaline Condition.
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24 (a) (b)
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26 Scheme 1. Chemical Structures of MO (a) and MB (b).
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29 SO3Na SO3Na
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31
32
33
34
35 NH OH- N
36
N H+ N
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38
39
40 Acidic(red)
Basic(yellow)
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42 N+(CH3)2
43
N(CH3)2
44
45 (a) quinone structure (b) azoic structure
46
47 Scheme 2. The Structure of Methyl Orange Under Acidic or Alkaline Condition.
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4 Figure captions:
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6 Figure 1. Images of finger citron, finger citron residues, and FAC.
7
8
9 Figure 2. N2 adsorption isotherms of activated carbon samples at 77 K.
10
11 Figure 3. Pore size distribution of activated carbon samples.
12
13
14 Figure 4. Effect of solution pH on adsorption amounts of the dyes. (C0 = 450 mg/L, T
15
16 = 318 K, stirring speed = 150 rpm, dose = 0.4 g/L).
17
18
19 Figure 5. Effect of amount of FAC on MB and MO dye solution adsorption. (C0 =
20
21 450 mg/L, T = 318 K, stirring speed = 150 rpm, dose = 0.4 g/L).
22
23
24 Figure 6. Figure 6. Adsorption isotherms of MO on FAC, NS-AC, CS-AC, W-AC
25
26 and C-AC, respectively. (t = 4 h, pH = 7, dose = 0.4 g/L, T=318 K).
27
28
29 Figure 7. Adsorption isotherms of MB on FAC, NS-AC, CS-AC, W-AC and C-AC,
30
31 respectively. (t = 4 h, pH = 7, dose = 0.4 g/L, T = 318 K).
32
33
34 Figure 8. Effect of contact time on the adsorption capacity of MO at different
35
36 temperature. (pH = 7, dose = 0.4 g/L ).
37
38
39 Figure 9. Effect of contact time on the adsorption capacity of MB at different
40
41
temperature. (pH = 7, dose = 0.4 g/L ).
42
43
44 Figure 10. Weber–Morris intra-particle diffusion plots for the adsorption of MO and
45
46
MB on FAC. (pH = 7, dose = 0.4 g/L ).
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48
49 Figure 11. Plot of In(Kd) versus 1/T for MO and MB adsorption on FAC (C0 = 450
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51
mg/L, time = 4 h, pH = 7, dose = 0.4 g/L).
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10 (a) Finger citron (b) Finger citron residues (c) FAC
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12
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14 Figure 1. Images of finger citron, finger citron residues, and FAC.
15
16
17 1100
18 FAC-1
1000
19
900
20
Volume adsorbed (cm /g)

800
3

21
22 700

23 600 W-AC
24 500
25 400 CS-AC
26
300
27 C-AC
200
28
29 100 NS-AC
30 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
31 Relative pressure (P/P0)
32
33
34
35 Figure 2. N2 adsorption isotherms of activated carbon samples at 77 K.
36
37
38 4.5
39
4.0 FAC
40 CS-AC
41 3.5 W-AC
42 C-AC
3.0 NS-AC
43
V (cm /g)

44 2.5
3

45 2.0
46
1.5
47
48 1.0

49 0.5
50
0.0
51 0 1 2 3 4 5 6 7 8 9 10
52 Pore size (nm)
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55 Figure 3. Pore size distribution of activated carbon samples.
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4 1000
5 MO
900
6 MB
7 800

Amount adsorbed (mg/g)

8 700
9
600
10
11 500
12 400
13
300
14
15 200
16 100
17
0
18 0 1 2 3 4 5 6 7 8 9 10 11
19 Initial pH of solution
20
21
22
23 Figure 4. Effect of solution pH on adsorption amounts of the dyes. (C0 = 450 mg/L, T
24
25 = 318 K, stirring speed = 150 rpm, dose = 0.4 g/L).
26
27
28 1000
29
900
30
Amount adsorbed (mg/g)

31 800
32 700
33
600
34
35 500

36 400
37
300
38
39 200

40 100
41 0
42 0.0 0.2 0.4 0.6 0.8 1.0 1.2

43 Amount of adsorbent (g/L)

44
45
46
Figure 5. Effect of FAC dose on adsorption of MB and MO dyes. (C0 = 450 mg/L, T
47
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49 = 318 K, stirring speed = 150 rpm, dose = 0.4 g/L).
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4 1000
5
900
6

Amount adsorbed MO, qe (mg/g)

7 800 FAC
W-AC
8 700 CS-AC
9 C-AC
600
10 NS-AC
11 500

12 400
13
300
14
15 200

16 100
17
0
18 0 50 100 150 200 250 300 350 400
19 Ce (mg/L)
20
21
22
23 Figure 6. Adsorption isotherms of MO on FAC, NS-AC, CS-AC, W-AC, and C-AC,
24
25 respectively. (t = 4 h, pH = 7, dose = 0.4 g/L, T=318 K).
26
27
28 600
29 550
30 500
Amount adsorbed MB, qe (mg/g)

FAC
31 W-AC
450
32 CS-AC
400
33 C-AC
34 350 NS-AC
35 300

36 250
37 200
38 150
39 100
40 50
41
0
42 0 30 60 90 120 150 180 210 240 270

43 Ce (mg/L)
44
45
46
Figure 7. Adsorption isotherms of MB on FAC, NS-AC, CS-AC, W-AC, and C-AC,
47
48
49 respectively. (t = 4 h, pH = 7, dose = 0.4 g/L, T = 318 K).
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3
4
5 900

Amount adsorbed MO, qt (mg/g)

800
7
700
8
9 600
10 303 K
500
11 308 K
12 400 313 K
13 318 K
300
323 K
14
200
15
16 100
17
0
18 0 20 40 60 80 100 120 140 160 180 200 220 240

19 Time (min)
20
21
22
23 Figure 8. Effect of contact time on the adsorption capacity of MO at different
24
25 temperature. (pH = 7, dose = 0.4 g/L ).
26
27
28 600
29
540
30
Amount adsorbed MB, qt (mg/g)

31 480
32 420
33 303 K
360
34 308 K
35 300 313 K
36 318 K
240 323 K
37
180
38
39 120
40 60
41
0
42 0 30 60 90 120 150 180 210 240
43 Time (min)
44
45
46
Figure 9. Effect of contact time on the adsorption capacity of MB at different
47
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49 temperature. (pH = 7, dose = 0.4 g/L ).
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4 1000
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900
6
7 800
8 700
9

qt (mg/g)
600
10
11 500
12 400
13 303 K (MO) 303 K (MB)
300 308 K (MO) 308 K (MB)
14
313 K (MO) 313 K (MB)
15 200
318 K (MO) 318 K (MB)
16 100 323 K (MO) 323 K (MB)
17
0
18 0 2 4 6 8 10 12 14 16
19 1/2
t (min )
1/2

20
21
22
23 Figure 10. Weber–Morris intra-particle diffusion plots for the adsorption of MO and
24
25 MB on FAC. (pH = 7, dose = 0.4 g/L ).
26
27
13
28
12 MO
29 MB
11
30
10
31
9
32
In (Kd)

8
33
7
34
6
35 5
36 4
37 3
38 2
39 1
40 0
0.00305 0.00310 0.00315 0.00320 0.00325 0.00330
41
(1/T) (1/K)
42
43
44 Figure 11. Plot of In(Kd) versus 1/T for MO and MB adsorption on FAC. (C0 = 450
45
46
mg/L, time = 4 h, pH = 7, dose = 0.4 g/L).
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