Adsorption of water from methanol solution using various adsorbent

Hendriyana, Bambang Hari Prabowo, Lulu Nurdini, and Gatot Trilaksono

Citation: AIP Conference Proceedings 1904, 020031 (2017);

View online: https://doi.org/10.1063/1.5011888
View Table of Contents: http://aip.scitation.org/toc/apc/1904/1
Published by the American Institute of Physics

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Adsorption of Water from Methanol Solution Using Various
Adsorbent

Hendriyanaa), Bambang Hari Prabowo, Lulu Nurdini, Gatot Trilaksono

Chemical Engineering Department, Faculty of Engineering, Universitas Jenderal Achmad Yani

a)
Corresponding author: hendriyana@lecture.unjani.ac.id

Abstract. Adsorption of water from methanol solution using batch and fixed-bed column with several adsorbents such as
MgSO4, Na2SO4, molecular sieve 3A and 4A was investigated. From a batch study, the results exhibited that the
adsorbents of moleculare sieve 3A > moleculare sieve 4A > Na2SO4 > MgSO4. Adsorption of water with all adsorbents
limited by mass transfer. The phenomenon of water adsorption process from methanol solution by using MgSO4.H2O and
Na2SO4 adsorbents can be well explained using Langmuir-Freundlich model. Langmuir-Langmuir-Freundlich two-site
model can be used to describe water adsorption events by molecular sieve 3A and 4A. From fixed bed study, the
breakthrough time increased with increasing bed height.

INTRODUCTION
Methyl formate is a raw material for formic acid, acetic acid, acetaldehyde, methyl acetate, ethylene glycol and
formamide. Production of methyl formate is dominated by methanol carbonylation [1]. The methanol used in the
process of carbonylation is essentially water-free (or preferably not more than 100 ppm by weight) [2]. Methanol
technical grade can be used as a reactant for the carbonylation process. However, these methanol has a water content
more than 100 ppm, so need a suitable method to reduce the water content of the methanol solution. The adsorption
process can be used to selective removal of water from methanol solution technical grade. Various adsorbents, such
as: salt (MgSO4 and Na2SO4) [3] and synthetic zeolites (3A and 4A molecular sieve) [3,4] can be applied in this
process.
Adsorbents of MgSO4 and Na2SO4 are chemical adsorbents that have very large water binding ability. According
to [5] the adsorbent of MgSO4.H2O and Na2SO4 has a water adsorption capacity of 0.65 g/g and 0.62 g/g,
respectively. For 3A and 4A molecular sieve has adsorption capacity 0.20 g/g and 0.21 g/g [6]. Performance and
phenomena of water adsorption in the liquid phase (methanol solution) using mentioned adsorbent still limited in the
literature. Therefore, the purpose of this study was to determine the best adsorbent of the above four adsorbents
based on the water removal efficiency and the ability to decrease the water content in the methanol solution. This
paper also presents an explanation of the adsorption phenomena for the four adsorbents based on kinetics model and
the adsorption isotherm model. In addition, this paper present the evaluation of the best adsorbent in the continous
mode.

METHODOLOGY

Material
Methanol technical-grade, MgSO4.7H2O and Na2SO4 were used in this work purchased from chemicals shop in
Bandung. Molecular sieve of 3A and 4A were used purchased from Sigma Aldrich.

Proceedings of the 3rd International Symposium on Applied Chemistry 2017

AIP Conf. Proc. 1904, 020031-1–020031-10; https://doi.org/10.1063/1.5011888
Published by AIP Publishing. 978-0-7354-1594-2/$30.00

020031-1
 Experiments
Activation of adsorbents

At first, adsorbent activated at high temperature for four hour. The activation process is carried out in an electric
furnace with heating rate 5oC/min. The temperature conditions for each of the adsorbents are presented in TABLE
1. The activation of MgSO4.7H2O at 105oC gives MgSO4.H2O.

TABLE 1 Temperature activation of adsorbents

No. Adsorbents Temperature (oC)

1 Na2SO4 105
2 MgSO4.7H2O 105
3 3A molsieve 200
4 4A molsieve 200

Batch adsorption experiments

An adsorption experiment was carried out with a batch operating model. In batch experiments, known amounts
of methanol solution technical-grade and adsorbent were charged into several 60 ml vials. Each vial contains 30.0
ml solution of methanol technical-grade with an initial concentration of water 2291 ppm-v and various of adsorbent
(0.5; 1; 2; 3 and 10 g). Then the vials were shaken at 120 rpm using an electric shaker at room temperature. The
liquid sample was analyzed using thermal conductivity of gas chromatography (GC) Shimadzu 14B. The column of
GC filled with Porapak-Q. The temperatures of the column oven, injector and detector were 150oC, 200oC and
200oC, respectively. Argon (99.9%) was used as a carrier-gas with flow rate of 15 cm3.s-1. The GC sample from
liquid a phase was taken using Hamilton micro syringe, and sample volumes about 0.5 micro liters. Time for
sampling of the liquid is about two hour. Liquid sample calibration performed using water+methanol solutions of
known concentrations. The area of the water peak was normalized to the methanol peak. Calculation of the quantity
of water in a sample was made based on the ratio of the peak areas of water and methanol.
The amount of water adsorbed onto adsorbent at any time (qt) was calculated from:

V (c0  ct )
qt  (1)
W
The amount of water adsorbed at equilibrium (qe) was calculated from:
V (c0  ce )
qe 
W (2)

For select the best adsorbent of water removal from methanol solution was used water removal efficiency
parameter. Water removal efficiency can be calculated as follows:
c0  ct
Water removal efficiency  x 100%
c0 (3)

where c0 , ct and ce are the initial concentration, concentration at any time and concentration at equilibrium of
water solution (g/L), respectively. V is the volume of the solution (L), and W is the mass of adsorbent (g).

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 Fixed bed experiments

The column were used in the continuous flow adsorption experiments has 1.4 cm inside diameter. The feed
methanol solution with concentration of water 100 g/L was dropwise from the top through the packed column (8, 26
and 32 cm), at average flow rates of 7 mL/min. Samples were collected from the exit of the column every 5 min and
analyzed for residual water concentration.

RESULTS AND DISCUSSION

Effects Of Contact Time

Fig. 1 show the effects of contact time to amount of water adsorbed (qt) and water removal efficiency. The
results showed that the uptake of water by four adsorbents is strongly depends on contact time.

MgSO4.H2O Na2SO4

4A molsieve 3A molsieve

FIGURE 1 Effects of contact time to amount of water adsorbed (qt) and water removal efficiency (Dosage of adsorbent: 333
g/L)

Based on the curve, the adsorbent has not reached saturation, thus for increase water removal efficiency and
decrease the water concentration in the solution below 100 ppm-v is with the add length of contact time. For 4A and
3A molecular sieve the adsorption of water was very rapid in the first 120 min. Then the adsorption of water
increased gradually until near equilibrium.

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 Effect of Adsorbed Amount
Effect of adsorbent dose to water removal efficiency shown in FIGURE 2. The water removal efficiency
increased rapidly with the increase in the adsorbent dose then increased slowly until reached equilibrium with the
further increase in the adsorbent dose. From Fig. 2 can be seen that at 17.0 g/L of the adsorbent dose, the water
removal efficiency reached 64.7% for MgSO4.H2O, 60.7% for Na2SO4, 85.0% for molecular sieve of 4A and 86.7%
for 3A. Water removal efficiency insignificant by increasing the amount of the adsorbent from 100 to 333 g/L, may
be due to the concentration of water in the solution as a driving force is not enough for mass transfer. The adsorbent
dose of 333 g/L gave the highest efficiency for four adsorbents, with the water removal efficiency for MgSO4.H2O,
Na2SO4, molecular sieve of 4A and 3A are 70.8, 72.9, 92.3 and 95.9%, respectively.

FIGURE 2 Effect of adsorbent dose to the water removal efficiency (Contact time: 480 min)

Effect of Adsorbent Type

Effect of adsorbent type to water removal efficiency and final water concentration in the methanol solution
shown in Fig. 3. Adsorbent dose use is 333 g/L and contact time is 480 min (8 hours). The final concentration of
water in the solution after contact with the adsorbent MgSO4.H2O and Na2SO4 for 8 hours was still high (>100
ppm-v). The highest water removal efficiency achieved by 3A molecular sieve is 96.0% with the final water
concentration 93 ppm-v. This concentration value is below the concentrations required by [2] for a carbonylation
process of 100 ppm-v. While molecular sieve 4A can only reduce up to 152 ppm-v. Molecular sieve 3A has a better
ability to be attributed more selectively. Where the size of the water molecule is smaller (2,9Å) compared with the
size of the pore molecular sieve 3A, and the larger molecular size of methanol (3.8Å) compared to the pore of
molecular sieve 3A.

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 FIGURE 3 Effect of adsorbent type to the water removal efficiency and final water concentration (Dosage of adsorbent: 333
g/L; Contact time: 480 min)

Kinetics of Isotherm Adsorption

For investigate the mechanism of the water adsorption process is controlled by mass transfer or chemical
reaction, then used pseudo-first-order and pseudo-second-order kinetics model. The differential equation for pseudo-
first-order and pseudo-second-order is the following equation (4) and (5), respectively.

dqt
 k1 (qe  qt )
dt (4)

dqt
 k 2 (qe  qt ) 2
dt (5)

With k1 is pseudo-first-order rate constant (min-1) and k2 is pseudo-second-order rate constant (g .g-1.min-1). The
pseudo-first-order and pseudo-second-order rate constants determined from Fig. 4 and Fig. 5 are presented in
TABLE 2. From Fig. 4 and 5 it can be seen that the most suitable kinetic model is the pseudo-firs-order kinetic
model. This indicates that the adsorption of water with MgSO4, Na2SO4, moleculare sieve 4A and 3A are limited by
mass transfer.

TABLE 2 kinetic parameters

No. Parameters MgSO4.H2O Na2SO4 4A molsieve 3A molsieve

1 k1 (min-1) 0.00360 0.00357 0.00559 0.00514
2 k2 (g.g-1.min-1) 0.27325 0.30487 0.30371 0.28021

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 MgSO4.H2O Na2SO4

4A molsieve 3A molsieve

FIGURE 4 Curve fitting of pseudo-firs-order kinetic model for various adsorbent (Dosage of adsorbent: 333 g/L)

MgSO4.H2O Na2SO4

4A molsieve 3A molsieve

FIGURE 5 Curve fitting of pseudo-second-order kinetic model for various adsorbent (Dosage of adsorbent: 333 g/L)

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 Equilibrium of Isotherm Adsorption
Adsorbent of MgSO4.H2O and Na2SO4

The mechanism of the water adsorption event of a methanol solution by using chemical adsorbents (MgSO4.H2O
and Na2SO4) can be explained using Langmuir and Langmuir-Freundlich adsorption isotherm model. The Langmuir
isotherm model assumes that a monolayer of adsorbed material (water) is adsorbed over a uniform adsorbent
surface. While, the Langmuir-Freundlich model presumes that the adsorption process takes place on a homogeneous
and heterogeneous surface. The Langmuir and Langmuir-Freundlich equation is shown in equation (4) and (5),
respectively.
kc
q  qS
1 k c (6)

k cn
q  qS
1 k cn (7)

where qS is the maximum capacity of adsorption (g/g), k (a constant related to the affinity of the binding sites,
L/mg) are the Langmuir isotherm constants, c is the concentration of water (g/L) and n is the adsorption intensity
and indicates both the relative distribution of energy and the heterogeneity of the adsorbent sites. The validation
curves of both models with the experimental results for each of the adsorbents are presented in Fig. 6 and the model
parameters are presented in Table 3.

TABLE 3 Isotherm adsorption parameters for MgSO4.H2O and Na2SO4

No. Models MgSO4.H2O adsorbent Na2SO4 adsorbent
1 Langmuir
k (g/L) 0.0113 0.0131
Error (%) 64 62
2 Langmuir-Freundlich
k (g/L) 274.6 0.358
n 35.7 7.9
Error (%) 38 9,3

Na2SO4
MgSO4.H2O

FIGURE 6 Curve fitting of a water adsorption curve at equilibrium condition by the Langmuir and Langmuir-
Freundlich for MgSO4.H2O and Na2SO4

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 From Fig. 6 can be seen that the Langmuir model for water adsorption using MgSO4.H2O and Na2SO4 adsorbents
can not describe the adsorption phenomena. The calculation from model deviated away from the experimental data
with an average relative error greater than 62%. The Langmuir-Freundlich model gives satisfactory results with an
average relative error of 38% for MgSO4.H2O and 9.3% for Na2SO4. The Langmuir-Freundlich model illustrates that
in the process of water adsorption of methanol solution using MgSO4.H2O and Na2SO4 forms monolayer on some
surfaces and multilayer on other surfaces.

Adsorbent of 3A and 4A Molecular Sieve

Mechanism of the water adsorption using 3A and 4A molecular sieve is described by a dual-site model . There
are two cavities in the pseudo unit cell, the α and β cages respectively, each of which is accessible to water [7,8,9].
Actually the model written on the original equation in [7,8] is a function of the partial pressure of water vapor. This
is due to the water adsorption conditions carried out on the vapor phase using a column with a fixed bed. While in
this study, water adsorption is carried out in the liquid phase. Thus the dual site model equation is modified into a
function of water concentration in the liquid phase as described in equation (6).

k  .c k . c
q  0,162 . q s  0,838 . q s
1 k  . c 1  k . c
(8)

where qs is the saturated adsorption capacity (g/g), k is the equilibrium constant for cage (L/g), k is the
equilibrium constant for cage  (L/g). The -Langmuir--Langmuir model's of validation results with experimental
data are presented in FIGURE 7. and parameters in TABLE 4.

TABLE 4 Isotherm adsorption parameters for 4A and 3A molecular sieve

No. Models 4A molsieve 3A molsieve
adsorbent adsorbent
1  Langmuir -  Langmuir
k 0.220 0.674
k 0.204 0.696
Error (%) 61.0 44.5
2  Langmuir -  Langmuir-Freundlich
k 0.433 2.518
k 474.9 1200
n 5.24 5.81
Error (%) 15.9 12.9
3  Langmuir-Freundlich -  Langmuir-Freundlich
k 12.2 399.9
k 320.6 999.9
n 4.81 5.42
Error (%) 14.2 38.2

020031-8
 FIGURE 7 Curve fitting of a water adsorption curve at equilibrium condition by two-site model for 4A
and 3A molecular sieve

From the curve it can be seen that the -Langmuir--Langmuir model's is not appropriate to describe the water
adsorption event of a methanol solution using molecular sieve. The average relative error for 4A molecular sieves is
61.0% and 3A is 44.5%. The -Langmuir--Langmuir model is further modified into -Langmuir--Langmuir-
Freundlich (-L --LF) and -Langmuir-Freundlich--Langmuir-Freundlich (-LF--LF).
The two-site model -L --LF and -LF--LF provide more satisfactory with an average relative error about
15%. The equilibrium constants on the  site for both models are much larger than the equilibrium constants on 
sites. This indicates that water is more adsorbed by the  site and only a small portion of the water adsorbed by the
 site. This is due to  sites have more number of cations than site  [9] .

Evaluation Of Moleculare Sieve 3A on Continous Mode

The best adsorbent based on the water removal efficiency achieved by 3A molecular sieve. The adsorption
breakthrough curves at different bed height from 8 to 32 cm with average flow rate 0,7 mL/min are given in
FIGURE 8. Breakthrough time for bed height 8 cm, 26 cm and 32 cm occurred after 20 min, 40 min and 45 min,
respectively.

FIGURE 8 Breakthrough curves expressed as Ce/Co versus time at different bed height

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 CONCLUSIONS
From batch experiments, the water removal efficiency and final water concentration in solution, it can be
concluded that the best adsorbent is 3A molecular sieve. The achievable efficiency is 95.9% with the final water
concentration of 92.87 ppm-v. The adsorbent dose used to achieve the condition was 333 g/L and with a contact
time of 8 hours. The phenomenon of water adsorption process from methanol solution by using MgSO4.H2O and
Na2SO4 adsorbents can be well explained using Langmuir-Freundlich model. Langmuir-Langmuir-Freundlich two-
site model can be used to describe water adsorption events by molecular sieve 3A and 4A. The fixed-bed column
breakthrough curves were analyzed at different bed depth where the breakthrough time increased with a increasing
bed depth from 8 to 32 mm.

ACKNOWLEDGEMENTS
This research was funded with Hibah Penelitian Produk Terapan 2017 from the Ministry of Research,
Technology and Higher Education.

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