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Acetic Acid Removal From Dilute Aqueous Solutions Using Zeolite 13X (#305990) - 345597 PDF
Acetic Acid Removal From Dilute Aqueous Solutions Using Zeolite 13X (#305990) - 345597 PDF
RESEARCH ARTICLE
Güler NARİN
Abstract: In this study, acetic acid adsorption equilibrium and kinetics of 13X synthetic zeolite
from aqueous solutions at 25, 35 and 45 °C were investigated. 13X particles (particle diameter
in the range of 75150 m) were contacted with different initial acetic acid cocentrations in
aqueous phases (0.23 wt. %) at constant temperature in a batch reactor. Acetic acid
concentrations of the liquid samples taken from the adsorption mixtures at specific time intervals
were measured by titration with NaOH solution and the time required for the system to reach
equilibrium and acetic acid amounts adsorbed at equilibrium were determined. The experimental
adsorption kinetics data was best represented by the pseudo-second order model and the model
parameters were calculated. The experimental equilibrium data was fitted to the Sips model and
the model parameters were calculated. Adsorption thermodynamic parameters (standard Gibbs
free energy change, enthalpy change, and entropy change of adsorption) were determined. The
acetic acid-saturated adsorbent was regenerated by two methods in order to evaluate its
reusability. Adsorption of acetic acid on 13X led to appearance of new bands in at 1390, 1472
and 1593 cm-1 in the transmittance infrared spectrum which were assigned to the acetate ions.
Regeneration of the acetic acid-saturated 13X in deionized water at 45 °C led to loss in intensities
of these bands indicating dissolution of the weakly adsorbed species associated with these bands.
After heating at 300 °C, the bands at 1472 and 1593 cm-1 disappeared whereas 1390 cm-1 band
remained and a very weak shoulder band appeared at 1720 cm-1.
Cite this: Narin G. REMOVAL OF ACETIC ACID FROM DILUTE AQUEOUS SOLUTIONS USING
ZEOLITE 13X. JOTCSB. 2017;1(2):159–90.
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INTRODUCTION
Acetic acid is one of the most important chemicals in the chemical industry and belongs to the
top 50 chemicals in amount produced (1). Acetic acid is used in the manufacture of vinyl acetate,
acetic anhydride, acetate esters, monochloroacetic acid, and as a solvent in the production of
dimethyl terephthalate and terephthalic acid (2). Worldwide acetic acid production between 2009
and 2014 had grown by an average of 3–4% per year, while world acetic acid capacity had grown
by an average of 4% per year. In 2010 world capacity exceeded 12 million tons/year (2). On an
industrial scale acetic acid is produced via the petrochemical route: Carbonylation of methanol,
liquid-phase oxidation of hydrocarbons, and oxidation of acetaldehyde (3). By 2012 ca. 90% of
acetic acid is manufactured by low-pressure methanol carbonylation technologies (2). In this
process, methanol and carbon monoxide are reacted in the liquid phase, with some water to
keep the catalyst in solution. After the reaction, a distillation column is employed to remove
methanol, water and carbon monoxide (4).
The increasing demand for acetic acid has led to an increase in the acetic acid amount in the
industrial wastewaters. Acids in wastewater are classified as priority pollutants and they must
be recycled, diluted or treated chemically and then degraded biologically. European countries
require neutralization or biological degradation of these waste streams (2).
Acetic acid concentrations in the waste streams and fermentation broths are usually lower than
5 wt. % (9-12). Separation of carboxylic acids from aqueous solution is necessary in
petrochemical manufacture, fermentation, and the environmentally and economically important
recovery from waste streams (13). The selection of an acetic acid separation method depends
on the economics. The conventional industrial method of carboxylic acid separation from the
fermentation broth is precipitation using calcium hydroxide. However this separation process
requires large amounts of sulfuric acid and generates solid waste in the form of calcium sulfate.
Conventional distillation is energy-intensive due to the small differences in the volatilities of
water and acetic acid. This separation process is economically viable provided that the acetic
acid is highly concentrated (1, 14, 15) at concentrations exceeding 70 wt. % (3).
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For separation of acetic acid from the dilute solutions, various other methods have been
investigated in recent years including solvent extraction (16), reactive extraction (10, 17-20),
pervaporation (14, 21-34) and electrodialysis (35-38). However most of these methods have
drawbacks such as high capital costs, low efficiency, complexity of operation, high chemical and
energy consumption as well as adverse environmental impact (39, 40).
Adsorptive separations can provide a viable option for separation of acetic acid from the dilute
aqueous solutions (41). The adsorption process allows flexibility in terms of both design and
operation. After adsorption, the adsorbent should be easily regenerated, thereby resulting in
significant cost savings. Activated carbons (15, 41-48), basic polymeric adsorbents (42, 45, 49-
51), ion exchangers (17, 52), silica gel (53), clays (54, 55), and carbon nanotubes (56) were
investigated as adsorbents for removal of acetic acid from the dilute aqueous solutions. Synthetic
zeolites (55, 57-60) and metal organic frameworks (61) are other adsorbents tested recently for
the adsorptive separation of acetic acid/water.
An energy-efficient cyclic process has been patented for the simultaneous removal and recovery
of acetic acid from water by concentration swing adsorption based on activated carbon
adsorbent. In this process the more adsorbable component is acetic acid, the less adsorbable
component is water, and the desorbent liquid is acetone (15).
The design and optimization of such a cyclic adsorptive separation process require determination
of the adsorption equilibrium and kinetic parameters. Furthermore, the ideal adsorbent should
have high adsorption capacity and selectivity, and be low-cost, easy to handle, environmentally
neutral, non-toxic, and easy to regenerate.
In the present study equilibrium and kinetics of adsorption of acetic acid on 13X was studied.
Several adsorption equilibrium and kinetic models were used to correlate the experimental data.
From the adsorption equilibrium studies at 25, 35 and 45C, the thermodynamic parameters
were determined. Two different regeneration methods were employed in order to test the
reusability of the adsorbent.
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Materials
Commercial synthetic zeolite 13X (Sigma-Aldrich, 3.2 mm pellets, Si/Al=1.2) was used as the
adsorbent in the present study. The extrudates were ground in a mortar and sieved to particle
diameter of 75150 m. Prior to the adsorption of acetic acid, these particles were activated in
a static oven at 320 °C for 24 hours.
Experimental procedure
The stock solution of acetic acid (Carlo Erba, glacial, %99.5100.5) was prepared by using
distilled water. The solutions which were used in the adsorption kinetic and equilibrium
experiments with the initial acetic acid concentrations in the range of 0.030.54 mol/L
(0.173.25 wt. %) were prepared by diluting the stock solution. Two grams of 13X were
contacted with 100 mL of acetic acid solutions of different initial concentrations in a thermostatic
water bath at 25, 35 and 45C at a shaking speed of 150 rpm. The samples which were taken
from the supernatant at specific times were titrated with 0.05 M aqueous NaOH solution in order
to determine the acetic acid concentration in the solution. The amount of acetic acid adsorbed
was calculated as follows:
qt Co Ct V
m (Eq. 1)
where qt is the amount of acetic acid adsorbed at the specified time, Co is the initial acetic acid
concentration of the solution, Ct is the acetic acid concentration in the solution at the specified
time, V is the volume of the solution, and m is the adsorbent mass.
Regeneration of the adsorbent is a critical step as it influences the overall economy of the
process. In order to test regenerability of the adsorbent, the 13X particles were saturated with
acetic acid, then washed with distilled water and dried in a static oven at 60 °C overnight. One
gram of these particles was then contacted with 50 mL of distilled water in the thermostatic
water bath at 45 °C. The samples which were taken at specific time intervals were titrated with
a NaOH solution in order to determine the amount of acetic acid desorbed. As another
regeneration method, the acetic acid-saturated 13X particles were kept in a static oven at 300
°C for 24 hours and were used in acetic acid adsorption at 25 °C again.
Adsorption Kinetics
During adsorption of acetic acid molecules in 13X, the acid molecules were first transferred from
the bulk solution to the external film surrounding the adsorbent particle (through the interparticle
pores), then through the external film and through the intraparticle pores. Then sorption occured
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at the adsorption sites by chemisorption or ion exchange or physisorption. The rate of sorption
might be controlled by the slowest mass transfer step.
In order to investigate the mechanism of adsorption of acetic acid in the 13X particles, the
pseudo-first-order (71), pseudo-second-order (72) and intraparticle diffusion (73) models were
employed. The model equations are given in Table 1.
Table 1: Adsorption kinetic models employed to the experimental kinetic data for acetic acid
adsorption in 13X.
Eqn.
Model Equation
number
qe qt logqe
log k1 t
Pseudo first-order (Eq. 2)
2.303
t 1 1t
Pseudo second-order (Eq. 3)
qt k2qe2 qe
Intraparticle diffusion qt ki t c (Eq. 4)
In these equations qt and qe are the amounts of acetic acid adsorbed at time t and equilibrium,
respectively, k1 is the pseudo-first-order rate constant for the adsorption process, k2 is the
pseudo-second-order rate constant for the adsorption process, ki is the intraparticle diffusion
constant, and c is the thickness of the boundary layer formed between the adsorbate molecules
and the adsorbent surface.
The goodness of fit was evaluated based on the linearity of the log(qe-qt) versus t, t/qt versus t
and qt versus t0.5 plots for the pseudo first-order, pseudo second-order and intraparticle diffusion
models, respectively.
Adsorption Equilibrium
Adsorption equilibrium isotherm describes how the adsorbate molecules distribute between the
liquid and the solid phases at equilibrium.
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qe qmasCe1 ns
1 ns
(Eq.
1 asCe
Sips (Langmuir–Freundlich)
101)
qmaTCe
Toth qe
1 aTCenT T
1n
(Eq. 11)
The equations for the adsorption equilibrium models given in Table 2 were fitted to the
experimental data using the Generalized Reduced Gradient (GRG) nonlinear regression
algorithm of Excel Solver. The model parameters minimizing the sum of the squares of the errors
(SSE) were calculated. The SSE values for the model fittings were calculated as follows:
SSE qe m 2
, o del qe ,e x p (Eq. 12)
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where qe,model and qe,exp are the calculated and experimentally measured adsorbate
concentrations at equilibrium, respectively.
Adsorption Kinetics
From the experimental adsorption kinetics data shown in Figure 1, it was concluded that the
equilibrium has been reached within the first 240 minutes. The acetic acid removal efficiency (%)
is calculated by following equation:
C C
%removal
efficiency
o e 100 (Eq. 13)
Co
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Figure 1: Variation of the amount of acetic acid adsorbed in 13X with time for different initial
acetic acid concentratons at (a) 25C, (b) 35C and (c) 45C.
The acetic acid removal efficiency of the 13X zeolite decreased with the initial acetic acid
concentrations but was not affected remarkably by the adsorption temperature as seen in Figure
2.
The values of the kinetic parameters (qe, k1, k2, ki, and c) and the regression coefficients (r2)
were determined from the intercepts and slopes of the linear plots using the corresponding
kinetic model equations in Table 1.
The regression coefficients (r2) calculated form the pseudo-first and pseudo-second order models
are given in Table 3. The correlation coefficients calculated for the pseudo-second order kinetic
model fitting are significantly higher than those obtained for the pseudo-first order kinetic model
for the whole acetic acid concentrations and temperatures indicating that the experimental
adsorption kinetic data can be represented by the pseudo-second-order kinetic model. This
revealed that the adsorption rate is controlled by a chemical reaction between the 13X surface
and acetic acid molecules involving valency forces through sharing or exchange of electrons
between sorbent and sorbate (72).
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Figure 2: Variation of the acetic acid removal efficiency with the initial acetic acid
concentration at 25, 35 and 45C.
Table 3: Comparison of the regression coefficients for linearized pseudo-first and pseudo-
second order kinetic models at various initial concentrations and temperatures.
25C 35C 45C
Pseudo- Pseudo- Pseudo- Pseudo- Pseudo- Pseudo-
Co (mol/L)
first second first second first second
order order order order order order
0.54 0.875 1.000 0.830 1.000 0.754 0.993
0.27 0.826 1.000 0.904 0.997 0.552 1.000
0.14 0.954 1.000 0.885 0.999 0.956 1.000
0.07 0.920 1.000 0.908 0.999 0.967 0.999
0.03 0.507 1.000 0.878 1.000 0.925 1.000
Figure 3: t/qt versus t plots for adsorption at (a) 25C, (b) 35C and (c) 45C.
The values qe and k2 calculated from the linear plots of t/qt versus t shown in Figure 3 are
presented in Table 4. The calculated qe values obtained from this model were in excellent
agreement with the experimental ones. The model represented the experimental data fairly well
in the whole concentration and temperature range of interest in the present study.
The pseudo-second order kinetic rate constant (k2) values were found to decrease while the
equilibrium adsorption capacities (qe) increased with the increasing initial acetic acid
concentration. The equilibrium sorption capacity (qe) did not change significantly with the
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temperature at the low initial acetic acid concentrations while it decreased with the increasing
temperature at the higher initial acetic acid concentrations. This suggested that the acetic acid
adsorption in 13X zeolite is favored at low temperatures and high initial acetic acid
concentrations.
From the qt versus t0.5 plots drawn according to the intraparticle diffusion model (for 35C shown
in Figure 4), it was found that all the plots exhibited three linear regions involved in adsorption
of acetic acid in 13X zeolite. The initial linear region where the adsorbed amount of acetic acid
increased rapidly corresponds to the adsorption on the external surface of the 13X particles. The
linear regions at later times where the adsorption occurs at a gradual rate represent adsorption
of the adsorbate molecules in the adsorbent particles (in mesopores between the zeolite crystals
and within the crystals) (73).
None of these plots passed through the origin (c is not equal to zero) implying that the
intraparticle diffusion was not the only rate-controlling step in the adsorption of acetic acid in
13X (73). The ki and c values calculated respectively from the slopes and intercepts of the linear
portions together with the regression coefficients (r2) for adsorption at 35C are given in Table
5. The ki values (rate of adsorption) at the later period of the adsorption were lower than those
at the beginning of the adsorption due to decrease in the mass transfer rate due to the low acetic
acid concentration left in the solution, i.e. lower driving force. The values of c decreased with
the decreasing initial acetic acid concentration.
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Figure 4: qt versus t0.5 plots for the acetic acid adsorption at 35 °C.
Table 5: Intraparticle diffusion control model parameters for the acetic acid adsorption at
35°C.
Co (mol/L) r2 ki (mmol/gmin0.5) c
1st linear region
0.54 0.911 0.373 3.414
0.27 0.997 0.573 2.570
0.14 0.892 0.635 1.684
0.07 0.952 0.541 0.554
0.03 0.978 0.185 0.329
2nd linear region
0.54 0.992 0.225 4.192
0.27 0.878 0.102 3.530
0.14 0.957 0.062 3.546
0.07 0.971 0.035 2.182
0.03 0.949 0.088 0.618
3rd linear region
0.54 0.771 0.020 5.600
0.27 0.989 0.015 4.937
0.14 0.767 0.007 4.106
0.07 0.109 0.001 2.602
0.03 0.650 0.003 1.057
Adsorption Equilibrium
The values of the model parameters and SSE for the adsorption equilibrium models are given in
Table 6. Considering these SSE values given in Table 6, it is evident that the experimental
equilibrium data can be represented better by the three-parameter models (R-P, Sips and Toth
models) than by the two-parameter models (Langmuir, Freundlich, Temkin and D-R models).
The SSE values for the Sips model were the lowest among those for the equilibrium models
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fitted. Thus it was concluded that the experimental adsorption equilibrium data can be
represented best with the Sips model.
Table 6: Adsorption equilibrium model parametres and SSE values for the fitted equilibrium
models.
Model Parameter 25°C 35°C 45°C
Langmuir qm 6.319 5.916 5.402
KL 47.316 61.926 73.708
SSE 0.750 0.343 0.217
Freundlich KF 8.30 7.89 7.15
nF 3.82 3.99 4.33
SSE 0.43 0.77 0.93
Temkin b 2.567 2.723 3.157
KT 1533.3 1520.1 1999.5
SSE 0.201 0.071 0.179
Dubinin-Radushkevich qmDR 6.265
KDR 0.0069
SSE 0.334 0.031 0.291
Redlich-Peterson KRP 1154.7 702.6 654.6
aRP 150.6 102.7 108.8
g 0.811 0.876 0.912
SSE 0.106 0.042 0.093
Sips qm 8.68 6.92 5.97
as 15.91 37.98 56.93
ns 1.90 1.53 1.41
SSE 0.061 0.012 0.022
Toth qm 11.112 7.485 6.222
aT 507.0 186.3 175.1
nT 0.311 0.491 0.580
SSE 0.068 0.015 0.038
Fitting of the Sips model to the experimental adsorption isotherms at 25, 35 and 45C are shown
in Figure 5. It can also be seen that the amount of acetic acid adsorbed at equilibrium decreased
with the increasing adsorption temperature.
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Figure 5: Experimental adsorption equilibrium data and the Sips model fittings.
The Sips model parameter characterizing the system’s heterogeneity (74) was found to decrease
with the increasing temperature suggesting that the system is "apparently" less heterogeneous
at higher temperatures. However, this does not point to what is the source of the heterogeneity,
whether it is the adsorbent structural property, the adsorbent energetical property or the sorbate
property (74).
The temperature dependence of the Sips model adsorption affinity constant (as) has the following
form (74):
Q RT
as as exp (Eq. 14)
where as is the affinity constant at infinite temperature and Q is the adsorption heat.
From the linear plot of lnas versus 1/T (Figure 6) (r2=0.965), the adsorption heat (Q) and aswere
calculated as 50.40 kJ/mol and 1.161010 L/mol, respectively. The calculated Q corresponds to
the isosteric heat at the fractional loading of 0.5 (74).
Zhang and co-workers stated that the experimental acetic acid adsorption isotherms for 13X
pellets (Si/Al<3) can be represented by the Freundlich model and determined the model
parameters as KF=1.20 mmol/g and nF=2.66 at 25C. The amount of acetic acid adsorbed
increased with the initial acetic acid concentration and temperature (endothermic adsorption).
The monolayer acetic acid adsorption capacity of was calculated as 6.38, 6.75 and 7.11 mmol/g
at 25, 35 and 45C, respectively, by the Langmuir model (60). The same research group had
found that the adsorbed amount of acetic acid decreased with increasing temperature, indicating
that acetic acid adsorption on UiO-66 was exothermic. The monolayer acetic acid adsorption
capacity of the MOF was calculated as 4.50 and 4.73 at 25 and 45C, respectively (61). The
monolayer acetic acid adsorption capacity of 13X used in the present study at 25C (6.32
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mmol/g) was shown to be in good agreement with that reported for the 13X pellets (Si/Al<3)
(6.38 mmol/g) (60), and higher than those of 330 resin (0.53 mmol/g) (75), activated carbon
(0.92 mmol/g) (48), multiwall carbon nanotube (0.09 mmol/g) (56) and UiO-66 (4.50 mmol/g)
(61).
Langmuir model constant, KL, indicates the affinity for the binding of acetic acid. A dimensionless
constant, commonly known as dimensionless separation factor (RL) can be represented as (76):
RL 1 (Eq. 15)
1 KLCo
The RL value indicates whether the adsorption is unfavorable (RL>1), linear (RL=1), favorable
(0<RL<1) or irreversible (RL=0) (77). In the present study, the RL values were found to vary
within the range of 0.026–0.434 indicating the favorable adsorption. The RL values decreased as
the temperature and initial acetic acid concentration increased (Figure 7).
Although it was found in the present study that the experimental adsorption equilibrium data
can be represented by the Sips model better, the monolayer adsorption capacity (qm) calculated
from the Langmuir model fitting was used to calculate the specific surface area (S) of the 13X
as follows:
where NA is Avogadro’s number and Aa is the cross-sectional area of the adsorbate molecule.
Assuming that the acid molecules are adsorbed vertically, with the alipatic chain up and the
carboxyl group down attached to the adsorbent surface, the cross-sectional area of a straight-
chain acid was taken to be about 2110-20 m2 (78). From the monolayer adsorption capacities
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were calculated from the Langmuir model fitting, the average specific surface area of the 13X
was calculated as 745 m2/g. This value fell in the range of the reported BET surface areas (500–
800 m2/g) measured with N2 adsorption data at -196 C for X and Y type zeolites (79).
Figure 7: Separation factor as a function of the initial acetic acid concentration and
temperature.
RT ln1 1
Ce (Eq. 17)
The experimental data and the D-R model fittings plotted using the model parameters given in
Table 6 were shown in Figure 8. Even though only one value of the characteristic energy was
used in the fitting of the experimental data at three temperatures, the fit is very good (r2=0.993)
demonstrating the effectiveness of this model in describing the experimental data for acetic acid
adsorption in 13X.
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The D-R model adsorption equilibrium constant KDR is related to the mean free energy of transfer
of one mole of solute from infinity in solution to the adsorbent surface as:
E 1
2KDR (Eq. 2)
This parameter gives information about the adsorption mechanism: If the magnitude of E is
between 8 and 16 kJ/mol the adsorption process follows by ion exchange, while the value below
8 kJ/mol the adsorption process is of a physical nature (85). In the present study the calculated
value of E (8.51 kJ/mol) is slightly above 8 kJ/mol suggesting that the removal of acetic acid
by 13X occurred by both physisorption and ion exchange mechanisms.
The micropore volume of 13X pellets was calculated as 0.359 cm3/g using the saturation
adsorption capacity corresponding to the D-R maximum pore volume (calculated from qmDR).
This value is in good agreement with the pore volume of NaX (Si/Al=1.25) determined from the
adsorption of different types of molecules including water, gases and hydrocarbon (0.25–0.36
cm3/g) in the literature (86).
Adsorption Thermodynamics
The change in the standard Gibbs free energy of adsorption (G) can be expressed as:
where K is the dimensionless equilibrium constant and 55.5 is the activity of water in solution.
K was determined from Ce versus Ce/qe plots. Temperature dependence of the dimensionless
adsorption equilibrium constant is given by the van’t Hoff equation,
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lnK ΔS ΔH
o o
(Eq. 4)
R RT
where H is the standard enthalpy of adsorption and S is the standard entropy of adsorption.
The values of H and S were calculated from the slope and intercept of the van’t Hoff plot
shown in Figure 9, respectively. The values of G, H and S are given in Table 7.
The negative G values indicated spontaneous adsorption of acetic acid on 13X zeolite. The
values of G° decreased from -19.52 to -22.00 kJ/mol with increase in temperature from 25C
to 45 °C indicating that the sorption of acetic acid was favorable at high temperatures. The
positive ΔH° values designated that the sorption of acetic acid in 13X was endothermic. However,
as previously stated and shown in Figure 5, the amount of acetic acid adsorbed at equilibrium
decreased with the increasing temperature. The reason for this is that in the low acetic acid
concentration range in which the dimensionless adsorption equilibrium constant (K’) was
calculated the amount of acetic acid adsorbed at equilibrium increased with temperature. This
indicates that the interaction between the acetic acid molecules and the 13X surface increased
with temperature in the low acetic acid concentration range, while weaker interaction between
the acetic acid and adsorbent than that between water and the adsorbent at high acetic acid
concentration range (87). The positive values of entropy change (ΔS°) implied the increased
randomness (degree of freedom of the system) at the solid-solute interface during adsorption,
which may be caused by the restricted mobility of acetic acid on the surface of 13X particles
compared with that of aqueous solution (88).
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Figure 11: Acetic acid adsorption kinetics for the fresh and heated (at 300C) 13X
after being saturated with acetic acid.
For regeneration of the acetic acid loaded activated carbons and macroreticular styrene-
divinylbenzene adsorbents, methanol, methyl acetate, and acetone were suggested as suitable
regeneration solvents (49). Lv and co-workers regenerated acetic acid-loaded ion exchange resin
with 2 to 4 % NaOH solution efficiently without harming the resin (75). In another study, a
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metal-organic framework (UiO-66) was washed with deionized water and ethanol, and reused in
acetic acid adsorption. After three adsorption-desorption cycles, the adsorption capacity of UiO-
66 decreased by 7% without any deformation in the structure of UiO-66 (61). Ethanol was
suggested as an adsorption-competitive solvent for the regeneration of the high-silica ZSM-5
powder (58). In fixed-bed separation process by concentration swing adsorption where activated
carbon was used as the adsorbent the bed was rinsed with acetone to displace acetic acid and
water from the bed (15). However, these regeneration processes increase the operational cost
and cause environmental pollution as they require use of chemicals. Acetic acid decomposes to
form CO2 and methane or to form ketene and water above 440 °C (89, 90). However this
temperature may harm the adsorbent concerning the regeneration temperature given by the
producer (91).
No significant changes neither in frequency nor in absorbance of the bands in the 400–1200 cm-
1
region was observed after the activation of 13X at 320 °C (Figure 12A, spectrum b). The
changes in bands in the the O–H stretching region are discussed below.
Upon adsorption of acetic acid from the solution with the initial acid concentration of 0.54 M at
25 °C resulted in a shift of the 966 cm-1 band to 1059 cm-1 and 1072 cm-1 band to 1156 cm-1
(Figure 12A, spectrum c). The frequency of 966 cm-1 band varies linearly with the number of
aluminum atoms in the framework tetrahedral sites (86). Thus the shift of 966 cm-1 band to a
higher frequency after the acetic acid adsorption indicated a decrease in the number of aluminum
atoms in the framework tetrahedral sites. Dealumination of zeolites is partially due to action of
proton. In acidic to neutral solutions, the protons in the solution can be adsorbed to the neutral
and negative surface groups and thereby protonate them (proton binding). The formation of the
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Figure 12: Absorbance IR spectra of 13X (A) 400–2000 cm-1 region and (B) 2000–4000 cm-1
region. (a) before activation, (b) after activation, (c) after acetic acid adsorption at 25C
(Co=0.54 M), (d) after desorption in deionized water at 45C and (e) after heating at 300C
subsequent to the adsorption.
Upon acetic acid adsorption, the bands at 467 cm-1 and 697 cm-1 lost intensity and the bands at
568 and 746 cm-1 disappeared. As mentioned above, the bands at 997, 697 and 467 cm-1 are
due to internal vibrations of the primary building units (TO4 tetrahedra) and are not sensitive to
structural variations while the bands at 746 and 568 cm-1 are sensitive to the linkages between
tetrahedra (external linkages). Thus it may be concluded that aluminum removal from the
framework sites upon acid adsorption led to changes in the external vibrations (secondary
structure, linkages between the tetrahedral units) but did not change the internal tetrahedral
vibrations significantly. The perturbations observed can be associated to T–O bond length, T–O–
T and O–T–O angles (93, 94). The disappearance of the band at 568 cm-1 suggested that the
external linkages were broken as a result of aluminum removal, i.e. that aluminum removal left
“holes” in the framework. Moreover, the formation of holes or the replacement of Al atoms by H
atoms involves changes in the frequencies and new bands or shoulders probably occur (95).
These perturbations created a new shoulder band at 900 cm-1.
Adsorption of acetic acid on 13X led to appearance of new bands in at 1390, 1472 and 1593 cm-
. The intensities of these bands were low since the acetic acid adsorption was performed in a
1
dilute acidic solution with low sorbent/solution ratio (2 g of sorbent/100 mL of solution). The
bands in the region of 1550–1610 cm-1 and 1300–1420 cm-1 were assigned to carboxylate
(carboxylic acid salt) while those in the 1700–1725 cm-1 region to carboxylic acid (96). The weak
band at 1390 cm-1 can be attributed to asymmetric deformation vibration of CH3. The band at
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1472 cm-1 and the shoulder at 1593 cm-1 may be assigned to the symmetric C–O stretching and
asymmetric stretching vibrations of the COO- group, respectively (97, 98).
Regeneration of the acetic acid-saturated 13X in deionized water at 45C was led to loss in
intensities of the bands at 1390, 1472 and 1593 cm -1 (Figure 12A, spectrum d) indicating
dissolution of the weakly adsorbed species were associated with these bands. Any significant
change was observed in the intensity or frequency of the bands in the 400–1400 cm-1 spectral
region.
In the spectra which were taken after heating at 300 °C (Figure 12A, spectrum e), the intensities
of the 467 and 697 cm-1 bands increased almost to their values in the spectrum for activated
13X and the bands at 568 and 746 cm-1 reappeared in the spectrum. The main asymmetric
stretching band at 1059 cm-1 was hifted back to 994 cm-1 and the asymmetric stretching band
(detected as a shoulder in the spectrum of 13X at 1072 cm -1) disappeared. These indicated the
reconstruction of the secondary building units. The bands at 1472 and 1593 cm-1 were
disappeared whereas 1390 cm-1 band was remained and a very weak shoulder band was
appeared at 1720 cm-1. In the literature the band at 1720 cm-1 was detected in the spectrum of
acetic acid dissolved in CCl 4 and assigned to the stretching vibrations of the C=O group (97, 99).
Evacuation of acetic acid vapor adsorbed NaHY at 200 °C led to a decrease in the intensity of
the typical bands of acetic acid (1690 and 1280 cm-1) and appearance of a doublet at 1580-1610
cm-1 and a band at 1480 cm-1. These new bands were similar to those in the spectrum of sodium
acetate. Evacuation at 300 °C resulted in a diminishing of the bands of unreacted acetic acid
molecules, without any decrease of the intensity of acetate ion bands. This suggested that
acetate ions formed in NaHY were stable until 300 °C (99).
The bands in this region are attributed to the OH bond stretching of the surface hydroxyl groups
or OH stretching mode of the water molecules (100). Surface hydroxyl groups in zeolites
originate from several sources: Acidic OH groups due to framework Al and other trivalent ions
such as B, Ga, Fe, etc.; silanol groups (Si–OH) on the external surface and in the “nests” (defect
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sites); OH groups attached to di- or tri-valent cations due to hydrolysis; OH groups from
“dangling Al”; OH groups associated with non-framework aluminum species and OH groups of
adsorbed water. The OH groups attached on the charge balancing ions formed via hydrolysis
can also be observed (101). The theoretical structure of X-type zeolite does not include any OH
groups. However cation deficient form of NaX may exhibit properties associated with hydroxyl
groups due to partial hydrolysis of the Na + cations and replacement by hydronium ions (86).
For the activated NaX, presence of various bands in the 3000-3800 cm-1 range of the spectra
was explained by the presence of several types of hydroxyl groups. The band at 3645 cm-1 was
assigned to free acidic OH groups bridging Al and Si atoms, pointing towards the supercages
(102, 103), while other types of acidic hydroxyls gave bands in the 3200-3600 cm-1 range (103).
These bands were related to cation deficiencies of NaX due to the fact that exchangeable cations
(e.g. Na+) were partially hydrolyzed during the preparation or the subsequent washing treatment
(104).
However in order to resolve the various OH groups, the adsorbed water must be removed so
the sample must be activated in situ. In the present study NaX was in fully hydrated state since
the acetic acid adsorption was studied in the aqueous solutions.
Zeolites always adsorb water when they are exposed to the atmosphere due to their hydrophilic
properties. The adsorbed water in zeolites can be present in the forms of free water, loosely
coordinated water, tightly coordinated water and even water clusters (105). Infrared
spectroscopic studies of water adsorption in faujasites revealed the existence of different
structures of adsorption complexes depending on the water loading (106-110). The water-
bending vibration at 1640 cm-1 indicates the presence of adsorbed water in zeolites. Due to the
hydrogen bonding of water with OH groups, the bands in the hydroxyl spectral region (3000–
4000 cm-1) are generally structureless and broad (101). Beta and co-workers reported a broad
band at about 3400–3500 cm-1 with a shoulder at about 3180–3250 cm-1 in the diffuse
reflectance infrared Fourier transform (DRIFT) spectra of the hydrated faujasites (including NaX).
The latter was assigned to the collective in-phase OH stretching vibrations of hydrogen bonded
aggregates consisting of a central water molecule and its nearest and higher neighbors. The
band at about 3400–3500 cm-1 was assigned to O-H stretchings of water molecules which are
hydrogen bonded to framework oxygen (107).
The intensity and width of the 3506 cm-1 band increased remarkably after the acetic acid
adsorption (Figure 12B, spectrum c). Intensity of this band decreased after the rinsing in water
without change in the width (Figure 12B, spectrum d). The intensity further declined and the
band has become less broadened upon heating at 300 °C (Figure 12B, spectrum e). The band
at 3506 cm-1 shifted to 3458 cm-1 after the acetic acid adsorption, to 3446 cm -1 after rinsing at
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45 °C in water and to 3493 cm-1 after heating to 300 °C. Upon acetic acid adsorption, a weak
band appeared at 2461 cm-1 and remained in the spectra after the rinsing of the acetic acid-
saturated 13X in distilled water and heating at 300 °C. A characteristic broad feature in the
range 3300–2500 cm-1, that overlaps the CH stretching region, and with a secondary absorption
close to 2600 cm-1, is observed for the hydrogen-bonded OH of most carboxylic acids. Other
bands that are associated with the CO and OH components of the carboxylic acid tend to be
less pronounced, and sometimes may be overlapped with other fingerprint absorptions of the
molecule. These are located in the ranges 1320–1210 cm-1 (CO stretch) and 960–850 cm-1
(hydrogen-bonded OH out-of-plane bending) (96).
Formation of acetate ions in NaHY was explained by the following reaction (99):
Upon the adsorption of acetic acid vapor on NaHY at 200 °C resulted in the removal of first 3640
cm-1 band (high frequency band, typical of Si–O1H–Al situated inside supercages) and then 3550
cm-1 band (low frequency band, typical of Si–O3H–Al situated inside hexagonal prisms). However
in the same study interaction of acetic acid vapor with Na+ ions in NaY did not result in any
important variation of the spectrum of the acetic acid solution suggesting molecular adsorption
of acetic acid in NaY. For NaY which usually does not contain SiOHAl groups, the acetate ions
were actually not formed. A small number of acetate ions formed in NaY was related to the
presence of very small amounts of extra framework Al species and/or a very small amount of
SiOHAl formed by the hydrolysis of NaY (99).
The shift of the 3506 cm-1 band to lower wavenumbers upon acetic acid adsorption and to higher
wavenumbers upon heating at 300 °C can be explained by the increased and decreased strength
of the water or acetic acid–framework oxygen hydrogen bonds, respectively. Beta and co-
workers observed a correlation between the position of the broad band at about 3400–3500 cm-
1
(assigned to OH stretchings of water molecules hydrogen bonded to framework oxygen) and
the basicity of framework oxygen atoms of NaX. The frequency of this band decreased with
decreasing water loading suggesting formation of more strongly bonded water-cation clusters
as a significant number of water molecules was removed (107).
The surface of the framework of 13X is essentially oxygen atoms, whereas Si and Al are buried
or recessed in the tetrahedra of oxygen atoms. They therefore are not fully exposed and cannot
be readily accessed by adsorbate molecules. Also, the anionic oxygen atoms are more abundant
and are much more polarizable than the Al and Si cations (79). In 13X, the framework oxygen
atoms which bear the negative charge of the lattice are considered as the structural basic sites.
Basic sites on oxide surfaces may be constituted by surface OH s- or Os2- anions. Acids which
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contain H-X functions are expected to undergo H-bonding interactions with basic surface sites
(111):
For weak interactions, the H-bond characteristics are the same as in the case of basic probe
molecules interacting with Brønsted acid sites. Therefore, frequency shifts of the H-X stretching
mode in the H-bonded complex relative to the free acid molecule must be induced and line
broadening and intensity enhancements must also occur (111).
In the present study, the bands detected in the 1200–1800 cm-1 after the acetic acid adsorption
indicated that adsorption of acetic acid in 13X resulted in formation of acetic acid ions (acetate,
CH3COO-). For 13X which usually does not contain SiOHAl groups, formation of the acetate
ions was not expected (99). However it was reported that NaX does not contain a total exchange
cation equivalency due to partial hydrolysis of the Na + cations and replacement by hydronium
ions. This cation deficient form of NaX may exhibit properties associated with hydroxyl groups
(86). Thus the formation of the acetate ions in 13X in the present study can be related to
presence of extraframework Al species and/or SiOHAl formed by the hydrolysis of 13X (99).
However it was not possible to follow the changes in the bands in the O–H stretching and H–O–
H bending regions upon the adsorption/desorption treatments performed since presence of water
in 13X complicated interpretation of the bands in these regions. The broad band in the O–H
stretching region of the hydrated 13X completely blanked out the spectral region.
In the literature Zhang and co-workers did not reported obvious changes in the SEM micrographs
and XRD patterns after interaction of 5 g of 13X zeolite (SiO2/Al2O3<3, in pellet and powder
forms) with 100 mL of aqueous acetic acid solutions with the initial concentrations of
0.0760.901 mol/L. The results verified that the 13X was stable when exposed to dilute acetic
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acid solution (60). Considering the lower initial concentrations of the acetic acid solutions (0.028-
0.544 mol/L) and lower adsorbent/solution ratio (2 g/100 mL) in the present study it is expected
that the 13X has chemical stability in the dilute acetic acid solutions.
CONCLUSION
It was shown that the kinetics of adsorption of acetic acid from diluted acetic acid solutions might
be represented by the pseudo-second order model and the model parameters were determined.
The adsorbed amount of acetic acid at equilibrium was decreased with the increasing adsorption
temperature. The adsorption equilibrium data was best described by the Sips model and the
model parameters were determined. The Sips model parameter characterizing the system
heterogeneity was found to decrease with the increased temperature. From the temperature
dependence of the Sips model adsorption affinity constant the isosteric heat at the fractional
loading of 0.5 was calculated as 50.40 kJ/mol. The monolayer acetic acid adsorption capacity of
13X at 25 °C was calculated as 6.32 mmol/g. The dimensionless separation factor values were
found to vary within the range of 0.026–0.434 indicating the favorable adsorption. The negative
G values indicated spontaneous adsorption of acetic acid on 13X zeolite. The positive ΔH°
values designated that the sorption of acetic acid in 13X was endothermic. However, as
previously stated, the amount of acetic acid adsorbed at equilibrium decreased with the
increasing temperature. The reason for that in the low acetic acid concentration range in which
the dimensionless adsorption equilibrium constant was calculated the amount of acetic acid
adsorbed at equilibrium increased with temperature. The positive values of entropy change was
implied the increased randomness (degree of freedom of the system) at the solid-solute interface
during adsorption. FTIR studies were revealed that the acetic acid adsorption was resulted in
formation of acetate ions. It was not possible desorb all the species formed by rinsing the acid-
saturated 13X in distilled water at 45C or by heating at 300C in air although removal of some
species was observed by FTIR spectroscopy.
ACKNOWLEDGEMENTS
The study presented here was perfomed as Graduation Project in 2015-16 Spring Term in
Department of Chemical Engineering, Uşak University. Part of the study was presented as a
poster in 12nd National Chemical Engineering Congress (23–26 August 2016, İzmir) and was
published in the Book of Proceedings. The author thanks to Burak Ertugrul and M. Murat Tercanli
for their help in the experimental work.
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REFERENCES
1. Huang RYM, Moreira A, Notarfonzo R, Xu YF. Pervaporation Separation of Acetic Acid-Water Mixtures
Using Modified Membranes .1. Blended Polyacrylic-Acid (Paa)-Nylon 6 Membranes. J Appl Polym Sci. 1988
Apr;35(5):1191-200. PubMed PMID: WOS:A1988M893700006. English.
2. C. Le Berre PS, P. Kalck, G.P. Torrence. Acetic Acid. Ullmann's Encyclopedia of Industrial Chemistry.
Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA; 2013.
3. King CJ. Acetic Acid Extraction. In: Lo TC, Baird,M. H. I., Hanson, C., editor. Handbook of Solvent
Extraction: Wiley; 1983. p. 567-72.
4. http://www.essentialchemicalindustry.org/chemicals/ethanoic-acid.html.
5. Lopez-Garzon CS, Straathof AJJ. Recovery of carboxylic acids produced by fermentation. Biotechnol Adv.
2014 Sep-Oct;32(5):873-904. PubMed PMID: WOS:000340696900001. English.
6. Palasantzas IA, Wise DL. Preliminary Economic-Analysis for Production of Calcium-Magnesium Acetate
from Organic Residues. Resour Conserv Recy. 1994 Jun 30;11(1-4):225-43. PubMed PMID:
WOS:A1994NY74000020. English.
7. Han IS, Cheryan M. Downstream processing of acetate fermentation broths by nanofiltration. Appl
Biochem Biotech. 1996 Spr;57-8:19-28. PubMed PMID: WOS:A1996UL85700004. English.
8. Straathof AJJ. Transformation of biomass into commodity chemicals using enzymes or cells. Chem Rev.
2014;114(3):1871-908.
9. Hong YK, Hong WH. Removal of acetic acid from aqueous solutions containing succinic acid and acetic
acid by tri-n-octylamine. Sep Purif Technol. 2005 Mar 15;42(2):151-7. PubMed PMID:
WOS:000227589900008. English.
10. Rasrendra CB, Girisuta B, van de Bovenkamp HH, Winkelman JGM, Leijenhorst EJ, Venderbosch RH, et
al. Recovery of acetic acid from an aqueous pyrolysis oil phase by reactive extraction using tri-n-octylamine.
Chem Eng J. 2011 Dec 1;176:244-52. PubMed PMID: WOS:000298900200033. English.
11. Keshav A, Wasewar KL, Chand S. Extraction of Propionic Acid From Model Solutions: Effect of pH, Salts,
Substrate, and Temperature. Aiche J. 2009 Jul;55(7):1705-11. PubMed PMID: WOS:000267475700008.
English.
12. Liu L, Zhu YF, Li JH, Wang M, Lee P, Du GC, et al. Microbial production of propionic acid from
propionibacteria: Current state, challenges and perspectives. Crit Rev Biotechnol. 2012 Dec;32(4):374-81.
PubMed PMID: WOS:000310708100005. English.
13. King CJ. Amine-Based Systems for Carboxylic-Acid Recovery. Chemtech. 1992 May;22(5):285-91.
PubMed PMID: WOS:A1992HU32900007. English.
14. Li SG, Tuan VA, Noble RD, Falconer JL. A Ge-substituted ZSM-5 zeolite membrane for the separation
of acetic acid from water. Ind Eng Chem Res. 2001 Dec 26;40(26):6165-71. PubMed PMID:
WOS:000172916100016. English.
15. Sircar S, inventor; Air Products and Chemicals, Inc., assignee. Separation of liquid mixtures by
concentration swing adsorption patent 5,026,482. 1991.
16. Kim GH, Park SJ, Um BH. Response surface methodology for optimization of solvent extraction to
recovery of acetic acid from black liquor derived from Typha latifolia pulping process. Ind Crop Prod. 2016
Oct 30;89:34-44. PubMed PMID: WOS:000381231000006. English.
17. Ahsan L, Jahan MS, Ni YH. Recovery of Acetic Acid from the Prehydrolysis Liquor of Kraft Based
Dissolving Pulp Production Process: Sodium Hydroxide Back Extraction from the Trioctylamine/Octanol
System. Ind Eng Chem Res. 2013 Jul 3;52(26):9270-5. PubMed PMID: WOS:000321541600064. English.
18. Yang G, Jahan MS, Ahsan L, Zheng LQ, Ni YH. Recovery of acetic acid from pre-hydrolysis liquor of
hardwood kraft-based dissolving pulp production process by reactive extraction with triisooctylamine.
Bioresource Technol. 2013 Jun;138:253-8. PubMed PMID: WOS:000320296600033. English.
184
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
19. Datta D, Kumar S, Uslu H. Status of the Reactive Extraction as a Method of Separation. J Chem-Ny.
2015. PubMed PMID: WOS:000352907900001. English.
20. Henczka M, Djas M. Reactive extraction of acetic acid and propionic acid using supercritical carbon
dioxide. J Supercrit Fluid. 2016 Apr;110:154-60. PubMed PMID: WOS:000370902300017. English.
21. Samanta HS, Ray SK, Das P, Singha NR. Separation of acid-water mixtures by pervaporation using
nanoparticle filled mixed matrix copolymer membranes. J Chem Technol Biot. 2012 May;87(5):608-22.
PubMed PMID: WOS:000302463000004. English.
22. Sun WG, Wang XW, Yang JH, Lu JM, Han HL, Zhang Y, et al. Pervaporation separation of acetic acid-
water mixtures through Sn-substituted ZSM-5 zeolite membranes. J Membrane Sci. 2009 Jun 15;335(1-
2):83-8. PubMed PMID: WOS:000266057600013. English.
23. Moulik S, Nazia S, Vani B, Sridhar S. Pervaporation separation of acetic acid/water mixtures through
sodium alginate/polyaniline polyion complex membrane. Sep Purif Technol. 2016 Oct 1;170:30-9. PubMed
PMID: WOS:000381950300004. English.
24. Kulkarni SS, Tambe SM, Kittur AA, Kariduraganavar MY. Preparation of novel composite membranes
for the pervaporation separation of water-acetic acid mixtures. J Membrane Sci. 2006 Nov 15;285(1-
2):420-31. PubMed PMID: WOS:000242209000046. English.
25. Yu J, Li H, Liu HZ. Recovery of acetic acid over water by pervaporation with a combination of
hydrophobic ionic liquids. Chem Eng Commun. 2006;193(11):1422-30. PubMed PMID:
WOS:000239382500006. English.
26. Kittur AA, Tambe SM, Kulkarni SS, Kariduraganavar MY. Pervaporation separation of water-acetic acid
mixtures through NaY zeolite-incorporated sodium alginate membranes. J Appl Polym Sci. 2004 Dec
5;94(5):2101-9. PubMed PMID: WOS:000224759700032. English.
27. Sano T, Ejiri S, Yamada K, Kawakami Y, Yanagishita H. Separation of acetic acid-water mixtures by
pervaporation through silicalite membrane. J Membrane Sci. 1997;123(2):225-33.
28. Netke SA, Sawant SB, Joshi JB, Pangarkar VG. Sorption and Permeation of Acetic-Acid through Zeolite
Filled Membrane. J Membrane Sci. 1995 Nov 15;107(1-2):23-33. PubMed PMID: WOS:A1995TF98100002.
English.
29. Yamanaka N, Itakura M, Kiyozumi Y, Ide Y, Sadakane M, Sano T. Acid stability evaluation of CHA-type
zeolites synthesized by interzeolite conversion of FAU-type zeolite and their membrane application for
dehydration of acetic acid aqueous solution. Micropor Mesopor Mat. 2012 Aug 1;158:141-7. PubMed PMID:
WOS:000305714200018. English.
30. Baruah K, Hazarika S. Separation of Acetic Acid from Dilute Aqueous Solution by Nanofiltration
Membrane. J Appl Polym Sci. 2014 Aug 5;131(15). PubMed PMID: WOS:000336456400058. English.
31. Lu SY, Chiu CP, Huang HY. Pervaporation of acetic acid/water mixtures through silicalite filled
polydimethylsiloxane membranes. J Membrane Sci. 2000 Aug 20;176(2):159-67. PubMed PMID:
WOS:000088820400002. English.
32. Deng SZ, Sourirajan S, Matsuura T. A Study of Polydimethylsiloxane Aromatic Polyamide Laminated
Membranes for Separation of Acetic-Acid Water Mixtures by Pervaporation Process. Sep Sci Technol.
1994;29(9):1209-16. PubMed PMID: WOS:A1994NT66200007. English.
33. Yoshikawa M, Kuno S, Wano T, Kitao T. Specialty Polymeric Membranes .4. Pervaporation Separation
of Acetic-Acid Water Mixtures through Modified Polybutadiene Membranes. Polym Bull. 1993
Nov;31(5):607-13. PubMed PMID: WOS:A1993MH90800015. English.
34. Liu Q, Noble RD, Falconer JL, Funke HH. Organics/water separation by pervaporation with a zeolite
membrane. J Membrane Sci. 1996 Aug 21;117(1-2):163-74. PubMed PMID: WOS:A1996UZ77500012.
English.
35. Yu LX, Guo QF, Hao JH, Jiang WJ. Recovery of acetic acid from dilute wastewater by means of bipolar
membrane electrodialysis. Desalination. 2000 Aug 10;129(3):283-8. PubMed PMID:
WOS:000088625900008. English.
185
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
36. Rehouma A, Belaissaoui B, Hannachi A, Muhr L. Bipolar membrane electrodialysis and ion exchange
hybridizing for dilute organic acid solutions treatment. Desalin Water Treat. 2013 Jan;51(1-3):511-7.
PubMed PMID: WOS:000313790300056. English.
37. Chukwu U, Cheryan M. Concentration of vinegar by electrodialysis. J Food Sci. 1996 Nov-
Dec;61(6):1223-6. PubMed PMID: WOS:A1996VZ33400026. English.
38. Jia YX, Chen X, Wang M, Wang BB. A win-win strategy for the reclamation of waste acid and conversion
of organic acid by a modified electrodialysis. Sep Purif Technol. 2016 Oct 17;171:11-6. PubMed PMID:
WOS:000383313300002. English.
39. Yu LX, Lin T, Guo QF, Hao JH. Relation between mass transfer and operation parameters in the
electrodialysis recovery of acetic acid. Desalination. 2003 Apr 15;154(2):147-52. PubMed PMID:
WOS:000181363500005. English.
40. Van der Bruggen B, Manttari M, Nystrom M. Drawbacks of applying nanofiltration and how to avoid
them: A review. Sep Purif Technol. 2008 Oct 22;63(2):251-63. PubMed PMID: WOS:000260702600003.
English.
41. Ganguly SK, Goswami AN. Surface diffusion kinetics in the adsorption of acetic acid on activated carbon.
Sep Sci Technol. 1996;31(9):1267-78. PubMed PMID: WOS:A1996UL35200005. English.
42. Munson CL, Garcia AA, Kuo Y, Frierman M, King CJ. Use of Adsorbents for Recovery of Acetic Acid From
Aqueous Solutions Part II – Factors Governing Selectivity. Separation & Purification Reviews.
1987;16(1):65-89.
43. Frierman M, Kuo Y, Joshi D, Garcia AA, King CJ. Use of Adsorbents for Recovery of Acetic-Acid from
Aqueous-Solutions .3. Solvent Regeneration. Separ Purif Method. 1987;16(1):91-102. PubMed PMID:
WOS:A1987J686500004. English.
44. Munson CL, Garcia AA, Kuo Y, Frierman M, King CJ. Use of Adsorbents for Recovery of Acetic-Acid from
Aqueous-Solutions .2. Factors Governing Selectivity. Separ Purif Method. 1987;16(1):65-89. PubMed
PMID: WOS:A1987J686500003. English.
45. Kuo Y, Munson CL, Rixev WG, Garcia AA, Frierman M, King CJ. Use of Adsorbents For Recovery of Acetic
Acid From Aqueous Solutions Part I – Factors Governing Capacity. Separation & Purification Reviews.
1987;16(1):31-64.
46. Park KM, Nam HG, Mun S. Adsorption equilibria of acetic acid on activated carbon. Korean Chemical
Engineering Research. 2015;53(1):127-30.
48. Dina DJD, Ntieche, A.R., Ndi, J.N., Ketcha Mbadcam J., . Adsorption of Acetic acid onto Activated
Carbons obtained from Maize cobs by Chemical Activation with Zinc chloride (ZnCl2). Research Journal of
Chemical Sciences. 2012;2(9):42-9.
49. Frierman M, Kuo Y, Joshi D, Garcia AA, King CJ. Use of Adsorbents for Recovery of Acetic Acid From
Aqueous Solutions Part Iii -- Solvent Regeneration. Separation & Purification Reviews. 1987;16(1):91-102.
50. Garcia AA, King CJ. Use of basic polymer sorbents for the recovery of acetic acid from dilute aqueous
solution. Industrial and Engineering Chemistry Research. 1989;28(2):204-12.
51. Gustafson RL, Albright RL, Heisler J, Lirio JA, Reid Jr OT. Adsorption of organic species by high surface
area styrene-divinylbenzene copolymers. Industrial and Engineering Chemistry Product Research and
Development. 1968;7(2):107-15.
52. Gregory J, Semmens MJ. Sorption of carboxylate ions by strongly basic anion exchangers. Journal of
the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1972;68:1045-
52.
53. Narges SL. Study of the Adsorption of Acetic Acid on Silica Gel in Aqueous Solution. Rev Roum Chim.
2013 Jan;58(1):43-+. PubMed PMID: WOS:000329771100006. English.
186
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
54. Morad Y, Hilali, M., Bazzi, L., Chaway, A. Elimination of organic pollutant (Acetic acid) by adsorption on
clays in aqueous solution: kinetic study and adsorption isotherms. Physical Chemistry: An Indian Journal
2014 2014;9(1):8-14.
55. Akbar S, Punnathanam, S., Pukala, M., . Adsorption of aqueous solutions of carboxylic acids on
montmorillonite, silicate, H-ZSM-5 and their Na+- and Li+-exchanged forms. Journal of The Chemical
Society Of Pakistan. 2008;30(5):664-73.
56. Ozcan O, Inci I, Asci YS. Multiwall Carbon Nanotube for Adsorption of Acetic Acid. J Chem Eng Data.
2013 Mar;58(3):583-7. PubMed PMID: WOS:000316307800010. English.
57. Bowen TC, Vane LM. Ethanol, acetic acid, and water adsorption from binary and ternary liquid mixtures
on high-silica zeolites. Langmuir. 2006 Apr 11;22(8):3721-7. PubMed PMID: WOS:000236745700043.
English.
58. Efe C, Van Der Wielen LAM, Straathof AJJ. High silica zeolites as an alternative to weak base adsorbents
in succinic acid recovery. Industrial and Engineering Chemistry Research. 2010;49(4):1837-43.
59. Faisal A, Zarebska A, Saremi P, Korelskiy D, Ohlin L, Rova U, et al. MFI zeolite as adsorbent for selective
recovery of hydrocarbons from ABE fermentation broths. Adsorption. 2014;20(2-3):465-70.
60. Zhang HH, Wang YM, Bai P, Guo XH, Ni XX. Adsorptive Separation of Acetic Acid from Dilute Aqueous
Solutions: Adsorption Kinetic, Isotherms, and Thermodynamic Studies. J Chem Eng Data. 2016
Jan;61(1):213-9. PubMed PMID: WOS:000368564600025. English.
61. Zhang HH, Lan XY, Bai P, Guo XH. Adsorptive removal of acetic acid from water with metal-organic
frameworks. Chemical Engineering Research & Design. 2016 Jul;111:127-37. PubMed PMID:
WOS:000380624300011. English.
62. Lipnizki F, Field RW, Ten PK. Pervaporation-based hybrid process: a review of process design,
applications and economics. Journal of Membrane Science. 1999 Feb 17;153(2):183-210. PubMed PMID:
WOS:000078138100005. English.
63. Feng XS, Huang RYM. Liquid separation by membrane pervaporation: A review. Ind Eng Chem Res.
1997 Apr;36(4):1048-66. PubMed PMID: WOS:A1997WR40200006. English.
64. Fleming HL. Consider membrane pervaporation. Chemical engineering progress. 1992;88(7):46-52.
65. Huang RY. Pervaporation membrane separation processes: Elsevier Science Ltd; 1991.
66. Morigami Y, Kondo M, Abe J, Kita H, Okamoto K. The first large-scale pervaporation plant using tubular-
type module with zeolite NaA membrane. Sep Purif Technol. 2001 Oct 1;25(1-3):251-60. PubMed PMID:
WOS:000171837900026. English.
67. Li G, Kikuchi E, Matsukata M. Separation of water-acetic acid mixtures by pervaporation using a thin
mordenite membrane. Sep Purif Technol. 2003;32(1-3):199-206.
68. Casado L, Mallada R, Téllez C, Coronas Jn, Menéndez M, Santamarı́a J. Preparation, characterization
and pervaporation performance of mordenite membranes. Journal of Membrane Science.
2003;216(1):135-47.
69. Li G, Kikuchi E, Matsukata M. A study on the pervaporation of water-acetic acid mixtures through ZSM-
5 zeolite membranes. J Membrane Sci. 2003;218(1-2):185-94.
70. Masuda T, Otani S, Tsuji T, Kitamura M, Mukai SR. Preparation of hydrophilic and acid-proof silicalite-
1 zeolite membrane and its application to selective separation of water from water solutions of concentrated
acetic acid by pervaporation. Sep Purif Technol. 2003;32(1-3):181-9.
71. Lagergren S. About the theory of so-called adsorption of soluble substances. 1898.
72. Ho YS, McKay G. Pseudo-second order model for sorption processes. Process Biochemistry. 1999
Jul;34(5):451-65. PubMed PMID: WOS:000081912700005. English.
187
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
73. Weber WJ, Morris JC. Kinetics of adsorption on carbon from solution. Journal of the Sanitary Engineering
Division. 1963;89(2):31-60.
74. Do DD. Adsorption Analysis: Equilibria and Kinetics:(With CD Containing Computer Matlab Programs):
World Scientific; 1998.
75. Lv HS, Sun YP, Zhang MH, Geng ZF, Ren MM. Removal of Acetic Acid from Fuel Ethanol Using Ion-
Exchange Resin. Energy & Fuels. 2012 Dec;26(12):7299-307. PubMed PMID: WOS:000312516400026.
English.
76. Weber TW, Chakravorti RK. Pore and solid diffusion models for fixed‐bed adsorbers. AIChE Journal.
1974;20(2):228-38.
77. McKay G, Blair HS, Gardner JR. Adsorption of dyes on chitin. I. Equilibrium studies. J Appl Polym Sci.
1982;27(8):3043-57.
78. Hansen RS, Craig RP. The adsorption of aliphatic alcohols and acids from aqueous solutions by non-
porous carbons. The Journal of Physical Chemistry. 1954;58(3):211-5.
79. Yang RT. Zeolites and Molecular Sieves. Adsorbents: Fundamentals and Applications: John Wiley &
Sons, Inc.; 2003. p. 157-90.
80. Dubinin M, Radushkevich L. Equation of the characteristic curve of activated charcoal. Chem Zentr.
1947;1(1):875.
81. Svilović S, Rušić D, Žanetić R. Thermodynamics and adsorption isotherms of copper ions removal from
solutions using synthetic zeolite X. Chemical and Biochemical Engineering Quarterly. 2008;22(3):299-305.
82. Arslan A, Veli S. Zeolite 13X for adsorption of ammonium ions from aqueous solutions and hen
slaughterhouse wastewaters. Journal of the Taiwan institute of chemical engineers. 2012;43(3):393-8.
83. Quintelas C, Pereira R, Kaplan E, Tavares T. Removal of Ni (II) from aqueous solutions by an
Arthrobacter viscosus biofilm supported on zeolite: from laboratory to pilot scale. Bioresource Technol.
2013;142:368-74.
84. Kim B, Lee H, Moon H, Lee K. Adsorption of radionuclides from aqueous solutions by inorganic
adsorbents. Separation science and technology. 1995;30(16):3165-82.
85. Dubinin M. The potential theory of adsorption of gases and vapors for adsorbents with energetically
nonuniform surfaces. Chemical Reviews. 1960;60(2):235-41.
86. Breck DW. Zeolite Molecular Sieves: Structure, Chemistry and Use1974. null p.
87. Jung BK, Hasan Z, Jhung SH. Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water
with a metal-organic framework. Chem Eng J. 2013 Dec;234:99-105. PubMed PMID:
WOS:000328588300013. English.
88. Lin S, Song Z, Che G, Ren A, Li P, Liu C, et al. Adsorption behavior of metal–organic frameworks for
methylene blue from aqueous solution. Micropor Mesopor Mat. 2014;193:27-34.
89. Blake P, Jackson G. The thermal decomposition of acetic acid. Journal of the Chemical Society B:
Physical Organic. 1968:1153-5.
90. Bamford C, Dewar M. 608. The thermal decomposition of acetic acid. Journal of the Chemical Society
(Resumed). 1949:2877-82.
91. Sigma-Aldrich. 13X product information sheet [cited 2017 01 Feb]. Available from:
https://www.sigmaaldrich.com/content/dam/sigma-
aldrich/docs/Sigald/Product_Information_Sheet/1/208582pis.pdf.
92. Stumm W, Morgan JJ. Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters
{Environmental Science and Technology}: Wiley; 1996.
93. Van Santen R, Vogel D. Lattice dynamics of zeolites. Adv Solid-State Chem. 1989;1:151-224.
188
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
94. Jacobs W, Van Wolput J, Van Santen R. An in situ Fourier transform infrared studyof zeolitic vibrations:
Dehydration, deammoniation, and reammoniation of ion-exchanged Y zeolites. Zeolites. 1993;13(3):170-
82.
96. Coates J. Interpretation of infrared spectra, a practical approach. Encyclopedia of analytical chemistry.
2000.
97. Bielański A, Datka J. Amphiprotic properties of OH groups in synthetic NaHY zeolites. Journal of
Catalysis. 1974;32(2):183-9.
98. Kubicki J, Schroeter L, Itoh M, Nguyen B, Apitz S. Attenuated total reflectance Fourier-transform
infrared spectroscopy of carboxylic acids adsorbed onto mineral surfaces. Geochim Cosmochim Ac.
1999;63(18):2709-25.
99. Kukulska-Zajac E, Gora-Marek K, Datka J. IR and TPD studies of the reaction of acetic acid in zeolites
NaHY. Micropor Mesopor Mat. 2006 Nov 26;96(1-3):216-21. PubMed PMID: WOS:000242229200030.
English.
100. Ma YN, Yan CJ, Alshameri A, Qiu XM, Zhou CY, Li D. Synthesis and characterization of 13X zeolite
from low-grade natural kaolin. Adv Powder Technol. 2014 Mar;25(2):495-9. PubMed PMID:
WOS:000334729500004. English.
101. Liu X. Infrared and Raman spectroscopy. Zeolite Characterization and Catalysis: Springer; 2009. p.
197-222.
102. Uytterhoeven J, Schoonheydt R, Liengme B, Hall WK. Studies of the hydrogen held by solids: XVI.
Infrared spectroscopy of X-and Y-type zeolites containing univalent and divalent cations. Journal of
Catalysis. 1969;13(4):425-34.
103. Jacobs P, Uytterhoeven J. Assignment of the hydroxyl bands in the infrared spectra of zeolites X and
Y. Part 1.—Na—H zeolites. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in
Condensed Phases. 1973;69:359-72.
104. Carter J, Lucchesi P, Yates D. The nature of residual OH groups on a series of near-faujasite zeolites.
The Journal of Physical Chemistry. 1964;68(6):1385-91.
105. de Mallmann A, Barthomeuf D. Change in benzene adsorption with acidobasicity of (Cs,Na)X zeolites
studied by i.r. spectroscopy. Zeolites. 1988 1988/07/01;8(4):292-301.
106. Bertsch L, Habgood H. An infrared spectroscopic study of the adsorption of water and carbon dioxide
by Linde molecular sieve X1. The Journal of Physical Chemistry. 1963;67(8):1621-8.
107. Beta IA, Bohlig H, Hunger B. Structure of adsorption complexes of water in zeolites of different types
studied by infrared spectroscopy and inelastic neutron scattering. Physical Chemistry Chemical Physics.
2004;6(8):1975-81.
108. Angell CL, Schaffer PC. Infrared Spectroscopic Investigations of Zeolites and Adsorbed Molecules. I.
Structural OH Groups1. The Journal of Physical Chemistry. 1965 1965/10/01;69(10):3463-70.
109. Hunger J, Beta IA, Böhlig H, Ling C, Jobic H, Hunger B. Adsorption Structures of Water in NaX Studied
by DRIFT Spectroscopy and Neutron Powder Diffraction. The Journal of Physical Chemistry B. 2006
2006/01/01;110(1):342-53.
110. Martra G, Coluccia S, Davit P, Gianotti E, Marchese L, Tsuji H, et al. Acidic and basic sites in NaX and
NaY faujasites investigated by NH3, CO2 and CO molecular probes. Research on Chemical Intermediates.
1999;25(1):77-93.
111. Knözinger H, Huber S. IR spectroscopy of small and weakly interacting molecular probes for acidic
and basic zeolites. Journal of the chemical society, faraday transactions. 1998;94(15):2047-59.
189
Narin, JOTCSB. 2017; 1(2): 159-190. RESEARCH ARTICLE
112. Przystajko W, Fiedorow R, Dalla Lana IG. Base properties of zeolite catalysts. Zeolites. 1987
9//;7(5):477-81.
113. Ciambelli P, Corbo P. Acid-base properties of zeolites by acetic acid temperature programmed
desorption. Thermochim Acta. 1988;137(1):51-8.
190