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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 28 February 2015
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 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Oyster shell reserved.
Prediction
http://dx.doi.org/10.1016/j.jiec.2015.02.021
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
242 H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 241–246
solute concentration. However, few studies have sought to Substituting Eq. (4) into Eq. (1) gives the second order function
directly predict removal efficiencies of adsorption processes as in which Ce is a one argument variable as follows:
functions of both initial solute concentration and adsorbent
K L qmax M
mass—information that could be conveniently applied to real K L Ce2 þ 1 þ K L C0 Ce C0 ¼ 0 (5)
V
adsorption processes.
The objective of this study was to demonstrate how basic
Note that the resulting equation shown above is a form of
adsorption isotherms combined with simple mass balance can be
quadratic equation if all variables other than Ce are treated as
applied to predict removal efficiency or required adsorbent mass
constants, and thus Ce can be explicitly and simply solved by using
under given sets of initial conditions. The intrinsic parameters of
the following quadratic formula [22,23]:
Langmuir and Freundlich adsorption isotherms were first obtained
by fitting experimental data for the adsorption of orthophosphate ð1 þ ðK L qmax M=V Þ K L C 0 Þþ
and methylene blue onto oyster shell powder and PAC, respec- qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
tively. Even though only one isotherm for each adsorption ð1 þ ðK L qmax M=V Þ K L C 0 Þ2 þ 4K L C 0
Ce ¼ (6)
experiment need be determined for the predictions, experimental 2K L
data for different sets of initial adsorption conditions were
obtained to be compared to the predicted values. Finally, contour The resulting Ce is a function of C0 and M for a specific V with
plots of predicted removal efficiencies were generated using both parameters KL and qmax. Therefore, once KL and qmax are obtained
initial solute concentration and adsorbent mass as independent from a set of adsorption experiments, equilibrium solute
variables. concentrations can be estimated for the given initial solute
concentration and the adsorbent mass in a fixed volume, which
Model development can differ from the conditions in the experimental set used for
determining KL and qmax. If the removal efficiency by adsorption for
Langmuir isotherm water treatment is set to R, it can be expressed as
C0 Ce
R¼ (7)
The Langmuir isotherm, which assumes monolayer adsorption C0
onto an adsorbent surface, can be expressed by the following
equation [10]: and thus R is also a function of C0 and M (R = R(C0, M)) for a specific
V.
For the given initial solute concentration and target removal
K L Ce
qe qmax (1) efficiency, the model equation to predict the adsorbent concen-
1 þ K L Ce tration can also be obtained. Substituting Eqs. (4) and (7) into
where Ce is the solute, or so-called adsorbate, concentration in the Eq. (1) and arranging for M gives:
solution at equilibrium (mg/L), qe the solute mass adsorbed per
V R V R
unit adsorbent mass at equilibrium (mg/g), KL the constant of the M¼ þ C0 (8)
K L qmax ð1 RÞ qmax
Langmuir isotherm (L/mg), and qmax relates to the maximum
adsorption capacity (mg/g). The above equation may be reformu-
Note that the resulting Eq. (8) is an explicit equation in which M
lated in the form of the following linear equation:
is a function of C0 and R for a specific V with parameters KL and qmax
(M = M(C0, R)), and thus the required adsorbent mass can be simply
1 1 1 1 predicted from a set of an initial solute concentration and a desired
¼ þ (2)
qe K L qmax C e qmax removal efficiency (Fig. 1).
C 0 ¼ C e þ CeS (3)
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.
H.-K. Chung et al. / Journal of Industrial and Engineering Chemistry 28 (2015) 241–246 243
Freundlich isotherm can also be formulated as follows: analysis, and it was found that adsorption for 3 h was sufficient to
reach equilibrium. To test the validity of the developed model,
1
log qe ¼ log C e þ log K F (10) additional adsorption tests were carried out by changing the mass
n
of the oyster shell powder separately added to 0.050 L of 10, 30, 60
Similar to the Langmuir adsorption isotherm, the above linear and 90 mg/L orthophosphate solutions. The oyster shell powder in
form of the equation can be used to evaluate whether the each sample was filtered out using 0.45-mm syringe filters.
adsorption process satisfies the Freundlich isotherm and to A total of 0.20 g of PAC was added to 0.40 L of each 25 to
identify the constants. If the experimental results show appreci- 450 mg/L methylene blue solution. Again, to verify the validity,
able linearity according to the equation, the adsorption process additional adsorption tests were conducted under different initial
may be deemed to follow the Freundlich adsorption isotherm. conditions. The mixtures were well agitated at 25 8C for 24 h using
The Freundlich isotherm was reformulated with mass balance. a mechanical shaker. The PAC was filtered from each sample using
Substituting Eq. (4) into Eq. (9) gives a 0.45-mm syringe before measuring absorbance in order to
evaluate the equilibrium concentration of methylene blue.
K F M 1=n
Ce þ C e C 0 ¼ 0 (11)
V
Parameter determination and model calculation
in which Ce is the one argument variable. Even though Eq. (11) is
not an explicit one and should be solved by using the numerical The isotherms were fitted to experimental data for orthophos-
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
parameters KF and 1/n. Therefore, with Eq. (7), R = R(C0, M) again. parameters. Those for methylene blue were fitted by non-linear
The mass of the adsorbent necessary for the desired removal regression using Eqs. (1) and (9) with a software program
efficiency can also be derived as follows: (Datafit1, Oakdale Engineering, USA). Eq. (11) was solved by
V R numerical analysis based on the Newton-Rahphson method [26]
ð11=nÞ
M¼ C (12) utilizing a spreadsheet program (Excel1 with visual basic
K F ð1 RÞ1=n 0
applications, Microsoft, USA). Menu-driven software using the
in which M = M(C0, R) for a fixed V (Fig. 1). visual basic userform of the program was exclusively created,
In summary, we have shown that mathematical expressions which allowed input of the pre-determined parameters and the set
were derived from both Langmuir and Freundlich adsorption
isotherms combined with the basic mass balance of the solute
concentration in the system. Once isotherm parameters are
determined from an isotherm consisting of a set of experimental
data, (i) the final solute concentration in the solution and the
removal efficiency, or (ii) required adsorbent mass in a fixed
volume for a desired removal efficiency can be estimated from an
initial set of conditions. Fig. 1 shows simplified flowcharts for
prediction under two different sets of initial conditions: left- and
right-side flowcharts correspond to the (i) and (ii) cases,
respectively.
Adsorption experiments
Table 1
Adsorption isotherm parameters determined from experimental data plotted in Figs. 2 and 4.
of initial experimental conditions. Once the program was executed used as a model adsorbate, was tested to further validate the
after the desired variables were input, the outputs of typical prediction method using an isotherm with mass balance. Fig. 4
adsorption isotherm curve data and related plots were exported shows the experimental data of qe vs. Ce and the best-fitting
into the spreadsheet. The removal efficiency and/or the required isotherms (Eqs. (1) and (8)). Resulting parameters of the isotherms
adsorbent mass for a particular level of target efficiency were are listed in Table 1. Based on the residual sum of squares (RSSs)
calculated, yielding the results in the userform. calculated by summing squared errors between data points and
predicted values, the data were slightly better fitted to the
Results and discussion Langmuir isotherm in this case. Considering qmax of the Langmuir
isotherm and KF of the Freundlich isotherm, PAC capacity for
Adsorption of orthophosphate onto oyster shell powder adsorbing methylene blue was much greater than that of oyster
shell powder for adsorbing orthophosphate. The determined
Experimental data from tests of orthophosphate adsorption parameters were used as constants in the isotherms with mass
onto oyster shell powder were fitted to the linear forms of balance to predict removal efficiency or required adsorbent mass
isotherms (Eqs. (2) and (9)), which are graphically represented in for conditions other than those of the experiments described
Fig. 2. The results indicate that the Freundlich equation, rather than above.
the Langmuir equation, provided a good mathematical model to The prediction was compared to experimental data for
describe the adsorption equilibrium. From the slope and intercept validation (Table 2). When C0 = 313 mg/L for methylene blue
of the plot of log qe against log Ce in Fig. 2(b), the KF and 1/n values and M = 0.41 g for PAC in 0.4 L, removal efficiencies were predicted
were obtained as listed in Table 1. to be 96.9% and 89.2% by the models based on the Langmuir and
Once the isotherm parameters were determined, the removal Freundlich isotherms, respectively (Table 2(a)). The experimental-
efficiencies for any set of experimental conditions could be ly determined value was 88.8%, and thus the prediction error was
predicted. Calculations using Eqs. (6) and (11) were executed to 9.12% and 0.45%. When C0 = 54.3 mg/L and M = 0.05 g in 0.5 L, the
obtain the predicted removal efficiencies as a function of the mass errors were 3.78% and 6.24%, respectively. These findings
of oyster shell powder for the different initial concentrations of demonstrate that once constants in the isotherm equations are
orthophosphates in the range of 10 to 90 mg/L. At the same time, determined with an experimental set under specific conditions, the
the predicted data were compared to the experimental data. Fig. 3 removal efficiency at different initial concentrations of solute and
shows that the predicted data were consistent with the adsorbent can be predicted without significant error by utilizing
experimental data. This indicates that the required adsorbent the model.
mass for any initial conditions could be pre-estimated prior to the In sequence, model verification was carried out in terms of
actual adsorption process. Although the plots of removal efficiency required adsorbent concentration (Table 2(b)). When C0 = 50 mg/L
as a function of the initial orthophosphate concentration for a fixed and target R = 95%, the required M was predicted to be around
adsorbent mass are not shown in this paper, the findings were 0.1 g/L for both models. For comparison, a batch adsorption test
similar. was conducted with C0 = 50 mg/L for methylene blue and M = 0.1 g
for PAC in V = 0.5 L. The experimental removal efficiency was
Adsorption of methylene blue onto PAC 95.6%. Therefore, calculations were repeated for C0 = 50 mg/L and
target R = 95.6%, and the results are presented in Table 2(b). The
Overall the adsorption capacity of oyster shell powder was very error was 19.1% and 6.00% for each model, respectively. Similarly,
low. Thus PAC adsorption of methylene blue, which is typically when the verification was tried once more for target R = 99.1% with
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.
(b) M prediction
Acknowledgements
References