G Model

JIEC 2430 1–6

Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

2 Application of Langmuir and Freundlich isotherms to predict

3 adsorbate removal efficiency or required amount of adsorbent
4 Q1 Hyung-Keun Chung, Woon-Hoe Kim, Jeongwon Park, Jinwoo Cho, Tae-Young Jeong,
5 Pyung-Kyu Park *
6 Department of Environmental Engineering, Yonsei University, 1 Yonseidae-gil, Wonju 220-710, Gangwon-do, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: The aim of this study was to investigate how basic adsorption isotherms could be applied to predict
Received 20 January 2015 removal efficiency or required adsorbent mass under given sets of initial conditions. The intrinsic
Received in revised form 23 February 2015 parameters of the Langmuir and Freundlich adsorption isotherms were experimentally obtained and
Accepted 23 February 2015
subsequently utilized to predict removal efficiencies for other sets of initial solute concentrations,
Available online xxx
solution volumes, and adsorbent masses, or to estimate the adsorbent mass required to remove solute at
a desired removal efficiency. This was accomplished by combining the isotherms with mass balance of
Keywords:
solutes between liquid solution and solid adsorbent phases.
Activated carbon
Adsorption isotherm
ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Oyster shell Chemistry.
Prediction

7
8 Introduction appropriate adsorption model was selected, the adsorption 30
parameters of the model were obtained and used to describe 31
9 Q3 Adsorption technology has been widely utilized in water and the adsorption characteristics. Langmuir-type adsorption is 32
10 wastewater treatment processes because it is a fast, effective, and considered to be a monolayer process. The maximum adsorption 33
11 relatively inexpensive method [1]. Organic and inorganic con- capacity per unit adsorbent mass is determined along with the 34
12 stituents in the water phase are effectively removed by adsorption Langmuir constant showing the solute affinity to the adsorbent. 35
13 technology [2–8]. Activated carbon such as granular and powdered Freundlich-type adsorption is considered to be a multi-layer 36
14 activated carbon (GAC and PAC) have been widely used as process in which the amount of adsorbed solute per unit adsorbent 37
15 adsorbent for water treatment [9–12], but because of considerable mass increases gradually. Freundlich parameters were also used 38
16 operating costs associated with regeneration and/or repeated to characterize the adsorption process. 39
17 injection, various alternative adsorbents have been studied [13– It should be pointed out that, in the adsorption isotherms, the 40
18 15]. Oyster shell powder containing calcium carbonate is one amount of adsorbed solute per unit adsorbent mass (dependent 41
19 such alternative. Large amounts of waste oyster shells are variable) is expressed as a function of the solute concentration 42
20 continuously generated in some countries, which offers a reliable at equilibrium (independent variable), not a function of initial 43
21 source for them to be used as a cheap adsorbent material [16,17]. It concentration. This implies that the model equation would only 44
22 was reported that the removal of orthophosphate by adsorption be utilized when the solute concentration at equilibrium is 45
23 onto oyster shell powder was comparable to that onto calcium known. However, in many practical adsorption studies and 46
24 carbonate [18]. industrial applications, it might be more desirable to predict the 47
25 In most adsorption studies, adsorption models such as removal efficiency for the given initial set of experimental 48
26 Langmuir and Freundlich isotherms have been widely used to conditions (initial solute concentration, solution volume, and 49
27 evaluate adsorption phenomena [10,19]. Generally, experimental adsorbent mass), or to estimate the adsorbent mass required to 50
28 data were fitted to adsorption isotherm models, and the best-fitted remove the solute for a desired removal efficiency. Najm et al. 51
29 model was used to characterize equilibrium adsorption. As the [20] reported the effect of initial di- and trichlorophenol 52
concentration on adsorption isotherm. Knappe et al. [21] 53
developed a method to predict PAC capacity for trace organic 54
compounds from initial solute concentration at a given adsorbent 55
* Corresponding author. Tel.:+82 33 760 2890.
E-mail addresses: pkpark@yonsei.ac.kr, pyungkyu.park@gmail.com (P.-K. Park). dose. Bolster [22] predicted adsorbed solute concentration as 56

http://dx.doi.org/10.1016/j.jiec.2015.02.021
1226-086X/ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021
 G Model
JIEC 2430 1–6

2 H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx

57 a function of initial solute concentration. However, few studies Substituting Eq. (4) into Eq. (1) gives the second order function 114
113
112
58 have sought to directly predict removal efficiencies of adsorption in which Ce is a one argument variable as follows: 115
59 processes as functions of both initial solute concentration and  
60 adsorbent mass—information that could be conveniently applied K L  qmax  M
K L  Ce2 þ 1 þ  K L  C0  Ce  C0 ¼ 0 (5)
61 to real adsorption processes. V
62 The objective of this study was to demonstrate how basic
Note that the resulting equation shown above is a form of 116
118
117
63 adsorption isotherms combined with simple mass balance can
quadratic equation if all variables other than Ce are treated as 119
64 be applied to predict removal efficiency or required adsorbent
constants, and thus Ce can be explicitly and simply solved by using 120
65 mass under given sets of initial conditions. The intrinsic
the following quadratic formula [22,23]: 121
66 parameters of Langmuir and Freundlich adsorption isotherms
67 were first obtained by fitting experimental data for the ð1 þ ðK L  qmax  M=V Þ  K L  C 0 Þþ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
68 adsorption of orthophosphate and methylene blue onto oyster
ð1 þ ðK L  qmax  M=V Þ  K L  C 0 Þ2 þ 4K L  C 0
69 shell powder and PAC, respectively. Even though only one Ce ¼ (6)
70 isotherm for each adsorption experiment need be determined 2K L
71 for the predictions, experimental data for different sets of initial The resulting Ce is a function of C0 and M for a specific V with 122
124
123
72 adsorption conditions were obtained to be compared to the parameters KL and qmax. Therefore, once KL and qmax are obtained 125
73 predicted values. Finally, contour plots of predicted removal from a set of adsorption experiments, equilibrium solute 126
74 efficiencies were generated using both initial solute concentra- concentrations can be estimated for the given initial solute 127
75 tion and adsorbent mass as independent variables. concentration and the adsorbent mass in a fixed volume, which 128
can differ from the conditions in the experimental set used for 129
76 Model development determining KL and qmax. If the removal efficiency by adsorption for 130
water treatment is set to R, it can be expressed as 131
77 Langmuir isotherm
C0  Ce
R¼ (7)
78 The Langmuir isotherm, which assumes monolayer adsorption C0
79 onto an adsorbent surface, can be expressed by the following
and thus R is also a function of C0 and M (R = R(C0, M)) for a specific 132
133
80 equation [10]:
V. 134
 
K L  Ce For the given initial solute concentration and target removal 135
qe  qmax (1)
1 þ K L  Ce efficiency, the model equation to predict the adsorbent concen- 136
tration can also be obtained. Substituting Eqs. (4) and (7) into 137
82
81 where Ce is the solute, or so-called adsorbate, concentration Eq. (1) and arranging for M gives: 138
83 in the solution at equilibrium (mg/L), qe the solute mass
84 adsorbed per unit adsorbent mass at equilibrium (mg/g), KL the V R V R
M¼ þ  C0 (8)
85 constant of the Langmuir isotherm (L/mg), and qmax relates to K L  qmax  ð1  RÞ qmax
86 the maximum adsorption capacity (mg/g). The above equation
Note that the resulting Eq. (8) is an explicit equation in which M 141
140
139
87 may be reformulated in the form of the following linear
is a function of C0 and R for a specific V with parameters KL and qmax 142
88 equation:
(M = M(C0, R)), and thus the required adsorbent mass can be simply 143
 
1 1 1 1 predicted from a set of an initial solute concentration and a desired 144
¼  þ (2) removal efficiency (Fig. 1). 145
qe K L  qmax C e qmax

89
91
90 In any adsorption experiments, Ce can be measured and qe Freundlich isotherm 146
92 can be calculated for a series of different conditions. Then
93 1/qe can be plotted as a function of 1/Ce. Note that most of the The Freundlich isotherm, which was originally developed as an 147
94 adsorption experiments have utilized the above linear form empirical model, may be written as follows [10,19]: 148
95 of the equation to evaluate whether or not the adsorption
1=n
96 process satisfies the Langmuir isotherm. If the resulting plot qe ¼ K F  Ce (9)
97 shows appreciable linearity, the adsorption process may be
where KF is the constant of the Freundlich isotherm (L1/n mg(11/n)/ 150
149
98 deemed to follow the Langmuir adsorption isotherm. Conse-
g), and 1/n is the Freundlich exponent. The linear form of the 151
99 quently two parameters (KL and qmax) can be obtained by using
100 the slope and the intercept to characterize the adsorption
101 process.
102 In this study, the isotherm equation was combined with a mass
103 balance, which has been generally used in modelling studies on
104 adsorption [10,19]. In a batch system at the given solution volume,
105 the following mass balance should be satisfied:

C 0 ¼ C e þ CeS (3)

106
107 where C0 is the initial concentration of solute in the solution, and CeS
108 is the concentration of solute adsorbed onto the adsorbent at
109 equilibrium. The qe in Eq. (1) can also be expressed in terms of
110 solution volume, V, and adsorbent mass, M, with C0 and Ce as
111 follows:

V  CeS V ðC 0  C e Þ Fig. 1. Simplified flowcharts for the application of adsorption isotherms combined
qe ¼ ¼ (4)
M M with mass balances to predict removal efficiency or required adsorbent mass.

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021
 G Model
JIEC 2430 1–6

H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx 3

152 Freundlich isotherm can also be formulated as follows: with periodic analysis, and it was found that adsorption for 3 h 207
was sufficient to reach equilibrium. To test the validity of the 208
1
log qe ¼ log C e þ log K F (10) developed model, additional adsorption tests were carried out 209
n by changing the mass of the oyster shell powder separately 210
155
154
153 Similar to the Langmuir adsorption isotherm, the above linear added to 0.050 L of 10, 30, 60 and 90 mg/L orthophosphate 211
156 form of the equation can be used to evaluate whether the solutions. The oyster shell powder in each sample was filtered 212
157 adsorption process satisfies the Freundlich isotherm and to out using 0.45-mm syringe filters. 213
158 identify the constants. If the experimental results show appreci- A total of 0.20 g of PAC was added to 0.40 L of each 25 to 214
159 able linearity according to the equation, the adsorption process 450 mg/L methylene blue solution. Again, to verify the validity, 215
160 may be deemed to follow the Freundlich adsorption isotherm. additional adsorption tests were conducted under different initial 216
161 The Freundlich isotherm was reformulated with mass balance. conditions. The mixtures were well agitated at 25 8C for 24 h using 217
162 Substituting Eq. (4) into Eq. (9) gives a mechanical shaker. The PAC was filtered from each sample using 218
a 0.45-mm syringe before measuring absorbance in order to 219
K F  M 1=n evaluate the equilibrium concentration of methylene blue. 220
Ce þ C e  C 0 ¼ 0 (11)
V
Parameter determination and model calculation 221
163
164 in which Ce is the one argument variable. Even though Eq. (11) is
165 not an explicit one and should be solved by using the numerical
The isotherms were fitted to experimental data for orthophos- 222
166 analysis method, Ce is a function of C0 and M for a specific V with
phate with linearized Eqs. (2) and (10) to determine isotherm 223
167 parameters KF and 1/n. Therefore, with Eq. (7), R = R(C0, M) again.
parameters. Those for methylene blue were fitted by non-linear 224
168 The mass of the adsorbent necessary for the desired removal
regression using Eqs. (1) and (9) with a software program 225
169 efficiency can also be derived as follows:
(Datafit1, Oakdale Engineering, USA). Eq. (11) was solved by 226
V R ð11=nÞ numerical analysis based on the Newton-Rahphson method [26] 227
M¼ C (12)
K F ð1  RÞ1=n 0 utilizing a spreadsheet program (Excel1 with visual basic 228
applications, Microsoft, USA). Menu-driven software using the 229
171
170 in which M = M(C0, R) for a fixed V (Fig. 1). visual basic userform of the program was exclusively created, 230
172 In summary, we have shown that mathematical expressions
173 were derived from both Langmuir and Freundlich adsorption
174 isotherms combined with the basic mass balance of the solute
175 concentration in the system. Once isotherm parameters are
176 determined from an isotherm consisting of a set of experimental
177 data, (i) the final solute concentration in the solution and the
178 removal efficiency, or (ii) required adsorbent mass in a fixed
179 volume for a desired removal efficiency can be estimated from an
180 initial set of conditions. Fig. 1 shows simplified flowcharts for
181 prediction under two different sets of initial conditions: left- and
182 right-side flowcharts correspond to the (i) and (ii) cases,
183 respectively.

184 Materials and methods

185 Materials and analytical methods

186 Oyster shell powder for the adsorption of orthophosphate was

187 prepared by thoroughly washing, drying, and grinding oyster shells
188 with a bench grinder [24]. Large particles were removed by using a
189 50-mesh sieve. Orthophosphate solution was prepared by dissol-
190 ving Na2HPO4 (Sigma-Aldrich Korea, Republic of Korea) in
191 deionized water. The concentration of orthophosphate was
192 measured by using the ascorbic acid method [25].
193 PAC (Duksan Pure Chemicals Co. Ltd., Republic of Korea) were
194 used as adsorbent. Methylene blue (Samchun Pure Chemicals Co.
195 Ltd., Republic of Korea) was used as solute to be adsorbed onto the
196 PAC, and its concentration was determined by measuring
197 absorbance at 664 nm with a spectrophotometer (8453 UV–vis,
198 Agilent Technologies, USA) after preparing a calibration curve
199 obtained with methylene blue solutions of known concentrations.

200 Adsorption experiments

201 Batch adsorption tests were conducted to determine param-

202 eters in isotherm equations. For orthophosphate adsorption,
203 1.0 g of oyster shell powder was placed in 0.050 L of solution Fig. 2. Experimental data of orthophosphate adsorption onto oyster shell powder
fitted to linearized forms of (a) Langmuir and (b) Freundlich isotherms (1.0-g oyster
204 containing orthophosphate ions in the range of 0 to 600 mg/L as shell powder in 0.050 L) where Ce is orthophosphate concentration in the solution at
205 P. The mixtures were then shaken vigorously in a mechanical equilibrium (mg/L) and qe is orthophosphate mass adsorbed per unit oyster shell
206 shaker at 25 8C. Adsorption was allowed to proceed up to 12 h powder mass at equilibrium (mg/g).

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021
 G Model
JIEC 2430 1–6

4 H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx

Table 1
Adsorption isotherm parameters determined from experimental data plotted in Figs. 2 and4.

Orthophosphate onto Methylene blue onto PAC

oyster shell powder

Langmuir isotherm KL (L/mg) 0.345 50.6

qmax (mg/g) 1.82 (R2 = 0.896) 298 (RSS1 = 5.71  104)
Freundlich isotherm KF (L1/n mg(11/n)/g) 0.500 214.50
1/n () 0.328 (R2 = 0.994) 0.0690 (RSS = 6.13  104)
1
Residual sum of squares.

231 which allowed input of the pre-determined parameters and the set used as a model adsorbate, was tested to further validate the 264
232 of initial experimental conditions. Once the program was executed prediction method using an isotherm with mass balance. Fig. 4 265
233 after the desired variables were input, the outputs of typical shows the experimental data of qe vs. Ce and the best-fitting 266
234 adsorption isotherm curve data and related plots were exported isotherms (Eqs. (1) and (8)). Resulting parameters of the isotherms 267
235 into the spreadsheet. The removal efficiency and/or the required are listed in Table 1. Based on the residual sum of squares (RSSs) 268
236 adsorbent mass for a particular level of target efficiency were calculated by summing squared errors between data points and 269
237 calculated, yielding the results in the userform. predicted values, the data were slightly better fitted to the 270
Langmuir isotherm in this case. Considering qmax of the Langmuir 271
238 Results and discussion isotherm and KF of the Freundlich isotherm, PAC capacity for 272
adsorbing methylene blue was much greater than that of oyster 273
239 Adsorption of orthophosphate onto oyster shell powder shell powder for adsorbing orthophosphate. The determined 274
parameters were used as constants in the isotherms with mass 275
240 Experimental data from tests of orthophosphate adsorption balance to predict removal efficiency or required adsorbent mass 276
241 onto oyster shell powder were fitted to the linear forms of for conditions other than those of the experiments described 277
242 isotherms (Eqs. (2) and (9)), which are graphically represented in above. 278
243 Fig. 2. The results indicate that the Freundlich equation, rather than The prediction was compared to experimental data for 279
244 the Langmuir equation, provided a good mathematical model to validation (Table 2). When C0 = 313 mg/L for methylene blue 280
245 describe the adsorption equilibrium. From the slope and intercept and M = 0.41 g for PAC in 0.4 L, removal efficiencies were predicted 281
246 of the plot of log qe against log Ce in Fig. 2(b), the KF and 1/n values to be 96.9% and 89.2% by the models based on the Langmuir and 282
247 were obtained as listed in Table 1. Freundlich isotherms, respectively (Table 2(a)). The experimental- 283
248 Once the isotherm parameters were determined, the removal ly determined value was 88.8%, and thus the prediction error was 284
249 efficiencies for any set of experimental conditions could be 9.12% and 0.45%. When C0 = 54.3 mg/L and M = 0.05 g in 0.5 L, the 285
250 predicted. Calculations using Eqs. (6) and (11) were executed to errors were 3.78% and 6.24%, respectively. These findings 286
251 obtain the predicted removal efficiencies as a function of the mass of demonstrate that once constants in the isotherm equations are 287
252 oyster shell powder for the different initial concentrations of determined with an experimental set under specific conditions, the 288
253 orthophosphates in the range of 10 to 90 mg/L. At the same time, the removal efficiency at different initial concentrations of solute and 289
254 predicted data were compared to the experimental data. Fig. 3 shows adsorbent can be predicted without significant error by utilizing 290
255 that the predicted data were consistent with the experimental data. the model. 291
256 This indicates that the required adsorbent mass for any initial In sequence, model verification was carried out in terms of 292
257 conditions could be pre-estimated prior to the actual adsorption required adsorbent concentration (Table 2(b)). When C0 = 50 mg/L 293
258 process. Although the plots of removal efficiency as a function of the and target R = 95%, the required M was predicted to be around 294
259 initial orthophosphate concentration for a fixed adsorbent mass are 0.1 g/L for both models. For comparison, a batch adsorption test 295
260 not shown in this paper, the findings were similar. was conducted with C0 = 50 mg/L for methylene blue and M = 0.1 g 296
for PAC in V = 0.5 L. The experimental removal efficiency was 297
261 Adsorption of methylene blue onto PAC 95.6%. Therefore, calculations were repeated for C0 = 50 mg/L and 298
target R = 95.6%, and the results are presented in Table 2(b). The 299
262 Overall the adsorption capacity of oyster shell powder was very error was 19.1% and 6.00% for each model, respectively. Similarly, 300
263 low. Thus PAC adsorption of methylene blue, which is typically when the verification was tried once more for target R = 99.1% with 301

Table 2
Comparison of (a) removal efficiency, R, and (b) required adsorbent mass, M, predicted by Freundlich isotherm with mass balance to experimental data points obtained from
adsorption of methylene blue onto PAC (a) R prediction.

Initial conditions Experimental R (%) Predicted R (%)

C0 (mg/L) M (g) Langmuir Error (%) Freundlich Error (%)

isotherm1 isotherm2

313 0.41 (in 0.4 L) 88.8 96.9 9.12 89.2 0.45

54.3 0.05 (in 0.5 L) 52.9 54.9 3.78 49.6 6.24

(b) M prediction

Initial conditions Experimental M (g) Predicted M (g)

C0 (mg/L) Desired R (%) Langmuir Error (%) Freundlich Error (%)

isotherm3 isotherm4

50.0 95.6 0.100 (for 0.5 L) 0.0809 19.1 0.106 6.00

314 99.1 0.496 (for 0.4 L) 0.420 15.3 0.540 8.87
1 2 3 4
Note: Calculated by using Eq. (6) with Eq. (7), Eq. (11) with Eq. (7), Eq. (8), and Eq. (12).

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021
 G Model
JIEC 2430 1–6

H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx 5

Fig. 3. Comparison of removal efficiency, R, predicted by Freundlich isotherm with

mass balance to experimental data points obtained at (a) 10, (b) 30, (c) 60, and (d)
90 mg/L orthophosphate ions as a function of oyster shell powder mass, M, in
0.050 L.

302 C0 = 314 mg/L, the errors between the predicted and experimental
303 values were 15.3% and 8.87%, respectively. Even though there were
304 errors between the predicted and experimental values for some
305 cases, overall the prediction of required adsorbent mass per known
306 solution volume without data fitting after parameter determina-
307 tion was reasonable at different initial concentrations of adsorbate
308 for target removal.

309 Practical application of the isotherms

310 For the oyster shell powder case, the Freundlich isotherm Fig. 5. Plots of (a) typical Freundlich isotherm calculated with equilibrium
311 simulated the experimental data better. Therefore, calculations orthophosphate concentration as independent variable and (b) removal efficiency,
312 were executed with the Freundlich isotherm in order to provide R, and equilibrium orthophosphate concentration, Ce, predicted with initial
orthophosphate concentration, C0, as independent variables (1-g oyster shell
313 useful information for the same set of initial experimental
powder in 1 L).
314 conditions. Fig. 5(a) shows a typical Freundlich isotherm graph,
315 which gives information only at equilibrium. Plots without initial Therefore, it is worth noting that the independent variable is the 320
316 concentration or adsorbent mass are less useful in terms of initial orthophosphate concentration instead of the concentration 321
317 practical applications because initial conditions are critical in at equilibrium in Fig. 5(b). Specifically, the equilibrium concentra- 322
318 preparation for injecting adsorbent with the aim of removing tion and removal efficiency by adsorption of 1-g oyster shell 323
319 solutes such as pollutants in water and wastewater treatment. powder in 1 L were predicted as a function of initial orthophos- 324
phate concentration. Similar to the oyster shell powder case, this 325
method was also used to predict the expected removal efficiency 326
from initial methylene blue concentrations, although the data are 327
not shown here. 328
Fig. 6(a) was generated by plotting the removal efficiency as a 329
function of independent variables, the initial methylene blue 330
concentration and PAC mass per 1 L (R = R(C0, M)). This figure 331
illustrates the practical application of adsorption isotherms—for 332
instance, M = 0.4 g results in an estimated 40% removal for 333
C0 = 308 mg/L (point A in Fig. 6(a)). Furthermore, when 90% and 334
99% removal efficiencies are required at C0 = 150 mg/L, M values of 335
0.52 and 0.67 g should be supplied per 1 L (points B and C in 336
Fig. 6(a)), respectively. In other words, 670 g of PAC should be 337
prepared to remove 99% of methylene blue from 150 mg/L solution 338
in a 1-m3 batch adsorption reactor. 339
Fig. 6(b) shows the orthophosphate case. From the plot, removal 340
efficiency can be visually estimated with different initial ortho- 341
phosphate concentrations and oyster shell powder masses. In 342
addition, the oyster shell mass required to reduce the orthophos- 343
Fig. 4. Data obtained from duplicate experiments of methylene blue adsorption phate to a desired level in a water treatment setting can be 344
onto PAC non-linearly fitted to Langmuir and Freundlich isotherms (0.20 g PAC in
predicted from the plot. For example, when a reduction in the 345
0.40 L) where Ce is methylene blue concentration in the solution at equilibrium and
qe is methylene blue mass adsorbed per unit PAC mass at equilibrium. The concentration from 5 to 0.05 mg/L is required, which corresponds 346
experiments were duplicated. to 90% removal, it is estimated that an M of 11.3 g should be 347

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021
 G Model
JIEC 2430 1–6

6 H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx

phases, the removal efficiency or required adsorbent mass was 356

successfully predicted using given sets of initial conditions. The 357
validity of the prediction method was verified by comparing the 358
predicted values to experimental data of orthophosphate adsorp- 359
tion onto oyster shell powder and methylene blue adsorption onto 360
PAC. The isotherm with mass balance enabled prediction of solute 361
concentration at equilibrium and removal efficiency by adsorption 362
using initial solute concentration and adsorbent mass per solution 363
volume. It also allowed estimation of the adsorbent mass required 364
for a target removal efficiency at an initial solute concentration, 365
implying that these models would be practically useful in 366
adsorption processes used for pollutant removal. 367

Acknowledgements 368

This work was supported by the Korea Ministry of Environment Q4 369

as ‘‘The Eco-Innovation project (Global Top Project) (no. GT-SWS- 370
11-02-007-6).’’ 371

References 372

[1] I. Ali, V.K. Gupta, Nat. Protoc. 1 (2006) 2661. 373

[2] N. Anderson, A.J. Rubin, Adsorption of Inorganics at Solid–Liquid Interfaces, Ann 374
Arbor Science Publishers, Inc., . Q5 375
[3] V.L. Snoeyink, ., McGraw-Hill, Inc, USA, 1990. Q6 376
[4] Q. Li, V.L. Snoeyink, B.J. Mariñas, C. Campos, Water Res. 37 (2003) 4863. 377
[5] E.W. Shin, J.S. Han, M. Jang, S.-H. Min, J.K. Park, R.M. Rowell, Environ. Sci. Technol. 378
38 (2004) 912. 379
[6] J. Rouquerol, F. Rouquerol, P. Llewellyn, G. Maurin, K.S. Sing, Adsorption by 380
Powders and Porous Solids: Principles, Methodology and Applications, Academic 381
Press, 2013. 382
[7] Y.C. Chen, C. Lu, J. Ind. Eng. Chem. 20 (2014) 2521. 383
[8] M. Khosravi, S. Azizian, J. Ind. Eng. Chem. 20 (2014) 2561. 384
[9] J.C. Crittenden, K. Vaitheeswaran, D.W. Hand, E.W. Howe, E.M. Aieta, C.H. Tate, M.J. 385
Mcguire, M.K. Davis, Water Res. 27 (1993) 715. 386
[10] J.C. Crittenden, R.R. Trussell, D.W. Hand, K.J. Howe, G. Tchobanoglous, MWH’s 387
Water Treatment: Principles and Design, Wiley, 2012. 388
[11] I.N. Najm, V.L. Snoeyink, B.W. Lykins Jr., J.Q. Adams, J. Am. Water Works Assn. Q7 389
(1991) 65. 390
[12] H. Sontheimer, J. Crittenden, R. Summers, American Water Works Association, 391
DVGW Forschungsstelle Engler Bunte Institute, Karlsruhe, 1988. 392
[13] D.R. Knappe, A. Rossner, S.A. Snyder, C. Strickland, Alternative Adsorbents for the 393
Removal of Polar Organic Contaminants, American Water Works Association, 394
2007. 395
[14] A. Rossner, S.A. Snyder, D.R. Knappe, Water Res. 43 (2009) 3787. 396
Fig. 6. Contour diagrams of removal efficiency, R, in % as a function of initial solute [15] G. Crini, Bioresour. Technol. 97 (2006) 1061. 397
concentration, C0, and adsorbent mass, M, (R = R(C0, M)) for adsorption of (a) [16] T.-C. Hsu, J. Hazard. Mater. 171 (2009) 995. 398
methylene blue onto PAC and (b) orthophosphate onto oyster shell powder in 1 L [17] Y.S. Ok, J.E. Lim, D.H. Moon, Environ. Geochem. Health 33 (2011) 83. 399
solution. [18] C. Namasivayam, A. Sakoda, M. Suzuki, J. Chem. Technol. Biotechnol. 80 (2005) 400
356. 401
[19] J.K. Edzwald, Water Quality & Treatment: A Handbook on Drinking Water, 402
348 supplied per 1 L (point D in Fig. 6(b)). Even though more precise McGraw-Hill, New York, NY, 2011. 403
349 values could be calculated by directly using the developed [20] I.N. Najm, V.L. Snoeyink, Y. Richard, J. Am. Water Works Assn. (1991) 57. 404
[21] D.R. Knappe, Y. Matsui, V.L. Snoeyink, P. Roche, M.J. Prados, M.-M. Bourbigot, 405
350 equations, plots similar to those in Fig. 6 would be practically Environ. Sci. Technol. 32 (1998) 1694. 406
351 useful for determining the trend in removal efficiency as a function [22] C.H. Bolster, J. Environ. Qual. 37 (2008) 1986. 407
352 of initial adsorption conditions at a glance. [23] M.K. Bothwell, L.P. Walker, Bioresour. Technol. 53 (1995) 21. 408
[24] W.-H. Kim, , Yonsei University, 2004 (Master’s Thesis). Q8 409
[25] APHA, Standard Methods for the Examination of Water and Wastewater, APHA, 410
353 Conclusions 1992. 411
[26] A. Ben-Israel, J. Math. Anal. Appl. 15 (1966) 243. 412
354 By combining Langmuir and Freundlich isotherms with mass
355 balance of solutes between liquid solution and solid adsorbent

Please cite this article in press as: H.-K. Chung, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.02.021