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# 2004 Institution of Chemical Engineers
www.ingentaselect.com=titles=02638762.htm Trans IChemE, Part A, July 2004
Chemical Engineering Research and Design, 82(A7): 855–864

SEPARATION OF ETHANOL–WATER MIXTURES USING

MOLECULAR SIEVES AND BIOBASED ADSORBENTS
S. AL-ASHEH*,{, F. BANAT and N. AL-LAGTAH
Department of Chemical Engineering, Jordan University of Science and Technology, Irbid, Jordan

T
he potential use of new biobased adsorbents and different types of molecular sieve was
assessed in the separation of the ethanol–water azeotrope. Molecular sieves of type 3A,
type 4A, and type 5A and biobased adsorbents such as natural corncobs, natural and
activated palm stone and oak, were used in this study. Each of these adsorbents was packed in
a column, which was surrounded by a heating jacket. The jacket temperature was maintained
constant in an attempt to maintain the packed-column at constant temperature. The water
concentration in the feed solution was varied from 5% to 12% (weight basis). Although the
initial concentration of ethanol in the flask was constant at the beginning of the experiment, it
varied with time due to boiling. The breakthrough curves of water sorption on these adsorbents
at different water contents showed that among the molecular sieves examined, type 3A
molecular sieves gave the best separation of the ethanol–water system and among biobased
adsorbents examined, natural palm stone was the best.
The Guggenheim, Anderson, and De Boer (GAB) model at different water contents
represented the isotherms for water sorption on molecular sieves and biobased adsorbents. In
addition, the surface area of adsorbents and maximum water uptake were calculated. Type 3A
molecular sieves were determined to have the largest surface area and the highest value of water
uptake compared with the other two types of molecular sieve. However, for the biobased
adsorbents, activated palm stone was found to have the largest surface area and the highest value
of water uptake compared to the other biobased adsorbents. It was found that upon activation, the
adsorption capacity of biobased adsorbents was not enhanced. On the contrary, the activation
gave negative results on some occasions.

Keywords: azeotrope; ethanol–water; molecular sieves; biobased sorbents.

INTRODUCTION
Ethanol is considered as one of the most useful synthetic
oxygen-containing organic chemicals. This is due to its unique
combination of properties as a solvent, a beverage, antifreeze,
a fuel, a depressant, and especially its versatility as a chemical
intermediate for other organic chemicals (Othmer, 1981).
Usually it is produced in an aqueous form either by
synthetic methods or fermentation processes. To obtain
pure ethanol, the conventional separation methods of
water removal include distillation processes. However,
these are inapplicable since at atmospheric pressure ethanol
forms an azeotrope with water at an ethanol composition of
95 wt% and a temperature of 78.1
C (Walas, 1985). There-
*Correspondence to: Dr S. Al-Asheh, Department of Chemical
Engineering, Jordan University of Science and Technology, PO Box 3030,
Irbid 22110, Jordan.
E-mail: alasheh@just.edu.jo
{
Currectly on sabbatical leave at Qatar University, Department of Chemical
Engineering, PO Box 2713, Doha, Qatar
E-mail: alasheh@qu.edu.qa
fore, special methods are used to break the azeotrope; these
include azeotropic distillation or extractive distillation where
ethylene glycol is added as a solvent (Treybal, 1980). In
addition, a membrane process known as pervaporation has
recently been used to break the ethanol–water azeotrope
using polyvinyl alcohol membranes (Cussler, 1997; Hickey
and Slater, 1990; Strathmann and Gudernatsch, 1991; Choi
et al., 1992; Bruschke, 1990). Pervaporation involves the
preferential passage of ethanol through a dense membrane
matrix. However, these polymeric membranes were not
found to be suitable for applications involving high water
concentrations or to de-water ethanol to very low dryness.
Zeolite-based membranes have been found efficient in
separating the ethanol–water azeotrope (Shah et al., 2000;
Nomura et al., 1998).
One of the methods used in separating water from ethanol
is adsorptive distillation. The adsorbents used are called
desiccants. These include molecular sieves, chloride salts,
silica gel, and biobased desiccants. Type A molecular sieves
are the most used in the application of ethanol–water
azeotrope separation. Sowerby and Crittenden (1998)
studied the recovery of ethanol from the ethanol–water
system at the azeotrope composition by adsorption using

855
856 S. AL-ASHEH et al.
fixed beds packed with various pore sizes of type A
molecular sieves. They found that type 4A are superior to
type 3A molecular sieves, with higher adsorption capacities,
while the type 5A molecular sieves were determined not to
be suitable since there is a great possibility of ethanol
adsorption within their pores. However, it was found that
the use of a type 3A molecular sieve for drying the ethanol–
water azeotrope instead of a type 4A is more efficient in
terms of energy saving since the regeneration energy
requirements for type 3A are lower than those of type 4A
(Trent, 1993).
It has been shown that biobased desiccants, which are
mostly composed of cellulose and starch, are also able to
remove water from a wide range of organics (Ladisch,
1997). Ladisch and Dyck (1979) first demonstrated the
separation of ethanol–water vapour mixtures over cracked
corn, starch and carboxymethyl cellulose, with a positive
energy balance compared with other adsorbents, such as
calcium oxide and sodium hydroxide. The authors found
that the total energy consumed for drying of ethanol by
calcium oxide is 3669 kJ kg1 ethanol, while the energy
consumed using cellouse is 2873 kJ kg1 ethanol (Ladisch
and Dyck, 1979). It was also found by the same authors that
the adsorption process using biobased adsorbents is more
energy-efficient than azeotropic distillation. The energy
consumption in azeotropic distillation for the ethanol–
water azeotrope is about 88 kJ m3 ethanol, which is
higher than the energy consumption needed for the adsorp-
tion process using corn grits by 32 kJ m3 ethanol (Ladisch
and Dyck, 1979). This indicates that the adsorption process
is less expensive than the azeotropic distillation process (Lee
and Ladisch, 1987). Corn grits are currently being used in
industry to dry over 750 million gallons of ethanol per year,
with 99.8% dryness by weight (Beery and Ladisch, 2001).
However, biobased desiccants are biodegradable and are
derived from renewable resources (Lee and Ladisch, 1987;
Beery and Ladisch, 2001).
In this work, new biobased desiccants that are able to
separate the azeotropic water–ethanol mixture are devel-
oped. Molecular sieves were taken as reference materials for
comparison purposes. The water content in the feed solution
was varied and the breakthrough behaviour at each water
concentration was determined. The isotherms of water
sorption are also presented and discussed at different inlet
water contents.
MATERIALS AND METHODS
Desiccants
Three different types of molecular sieve, namely type 3A,
type 4A, and type 5A, were used in this work. These were
purchased from Scharlau Chemie (Spain) and The Asso-
ciated Cement companies Ltd. (India). The molecular sieves
were dried in an oven at temperatures of 190–210
C for 24
hours. This is to make sure that all humidity within the
crystals of molecular sieves is evaporated (Trent, 1993). The
dried molecular sieves were kept in bottles, which then
were stored in a glass chamber. The glass chamber contained
silica gel to make sure that no humidity would be sorbed on
the molecular sieves.
Palm stones (date pits), oak, and corncobs were used in
this work as natural biobased adsorbents. The palm stone
Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
and oak were washed with distilled water and then dried in
an oven at temperatures of 70–80
C for 24 hours. The dried
natural palm stone and oak were crushed and dried again.
The dried palm stones and oak were crushed, milled and
sieved into different particle sizes. They were then kept in
bottles and stored in a glass chamber, which contained silica
gel. Studies were focused on the size fraction of 0.125–
0.212 mm. Corncobs were cut into small pieces with a knife
and washed with distilled water before being dried in a
packed bed using nitrogen at a temperature of 90
C for six
hours. This was to ensure that no biological degradation
occurred to the polysaccharides within the corncobs
(Westgate and Ladisch, 1993). The dried corncobs grits
were then kept in bottles that are stored in a glass chamber
containing silica gel.
Crushed palm stone and oak also underwent a physical
activation process using a vertical fluidized backed column
oven. The procedure of activation is summarized as follows.
The column was filled with the natural material. The
temperature of the bed was raised to 700
C, using electrical
heaters, in the presence of nitrogen gas at a flow rate of 1.5–
2.0 cm3 min1. The material was kept at 700
C for two
hours. After that, the temperature was raised to 900
C in the
presence of nitrogen gas. Pyrolysis gases were formed and
these were released to the atmosphere directly. When the
temperature reached 900
C, the nitrogen gas flow was
replaced by carbon dioxide gas for 30 minutes. At the
end, the heaters were switched off and cooling was allowed.
The activated materials were then removed from the column.
They were dried in the oven at temperatures of 190–210
C
for 24 hours to make sure that no humidity would be sorbed
on the activated materials during the cooling process. The
dried activated biobased adsorbents were kept in bottles that
were stored in a glass chamber containing silica gel. Raw
palm stones and activated palm stones have BET surface
areas of 1.56 and 870 m2 g1, respectively, and micropore
surface areas of 0.19 and 364 m2 g1, respectively (Guo and
Lua, 2001).
Bench-Scale Fixed Bed Adsorber
A bench-scale fixed bed adsorber apparatus has been
designed and is shown schematically in Figure 1. The
adsorbent was packed in the fixed bed (14.6 mm ID (internal
diameter); 25 cm depth). The column wall temperature was
maintained at the initial bed temperature during the experi-
ment by circulating hot water through the jacket. The jacket
was insulated with heating tape.
In a typical experiment, vapour was boiled up from a
500 ml flask surrounded by an electric heating mantle. Heat
input was controlled by a variable transformer. The tempera-
ture of the mixture in the boiling flask was measured by a
thermocouple. The atmospheric pressure was assumed
constant at 760 mmHg. The temperature of the jacket was
controlled and kept constant during the runs. The exit
stream was condensed using water as a cooling medium.
The condensate was removed every four minutes; a volume
of about 6 ml was collected. Thus, the average flow of the
condensate was about 1.5 ml min1. This was achieved by
controlling the heat input by manipulating the power supply.
A Karl Fischer titrator measured the water content of
the condensate. At the end of experiment, the adsorbent
was removed from the bed and dried for further use.
 SEPARATION OF ETHANOL–WATER MIXTURES USING MOLECULAR SIEVES
Figure 1. Schematic diagram of bench-scale fixed bed adsorber.
The adsorbents were efficient even after 10 cycles of the
adsorption–drying process.
The aqueous ethanol mixtures were prepared at four water
levels, namely, 5 (the azeotropic concentration), 8, 10, and
12 wt%. They were prepared by weighing the desired
amounts of distilled water and ethanol (Frutarom Ltd.,
UK) to make about 350 ml solution.
RESULTS AND DISCUSSION
Breakthrough Curves Using Molecular Sieves
Three molecular sieves of type A were used to study the
breakthrough behaviour, a sudden increase in water concen-
tration in the effluent, of water sorption using four different
water concentrations of ethanol–water mixtures. The break-
through curve of water sorption is plotted for the three
different pore sizes of molecular sieve at the different water
concentrations. The results are shown in Figure 2 for water
contents of 5, 8, 10, and 12 wt%, respectively.
It is seen (Figure 2) that the time required to reach a
plateau value varies as a function of the inlet water content
of ethanol–water mixture. Note that some curves do not
show the plateau behaviour since more time was required for
these curves to attain the plateau value and these data are not
shown. The time needed to reach a plateau value in the case
of 5 wt% was about 144 minutes. This is longer than that of
other water contents, which is about 120 minutes. It is also
Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
857
noted (Table 1) that the plateau time, time at which the water
content in the exit becomes the same as the inlet, becomes
shorter as the water concentration increases. This behaviour
is attributed to the fact that the 5 wt% water content
represents the azeotropic composition of the mixture; i.e.,
the compositions of ethanol and water in the liquid and
vapour phases are the same. The separation of ethanol from
water is only achieved by the selective sorption of the
molecular sieves used. It is also worth mentioning that
the breakthrough behaviour likely resulted in less than
complete water removal given that the column was relatively
short.
To distinguish between the three types of molecular sieve,
the average water content in the samples of the effluent
stream was considered as well as the calculated breakthrough
time for each type of molecular sieve used. The breakthrough
time is arbitrarily designated to be the time required to reach
2 wt% of water content in the effluent stream. This value was
chosen because it happens that water concentration in the first
droplet of condensate was greater than 1 wt% for some of the
sorbents. It is important to emphasize that the data are plotted
as water content in effluent stream divided by initial water
content (C=C0) versus time, therefore, the breakthough time
varies depending on the initial water content. A 2 wt% was
selected since the sorption of water on type 5A molecular
sieves usually gives outlet water content more than 1 wt%.
The average content of the effluent and the breakthrough time
for the different types of molecular sieve are displayed in
Table 1.
It can be concluded from the data of Table 1 that at a
given water content, type 3A molecular sieves has the best
sorption performance, followed by type 4A, and lastly by
type 5A. The longer the breakthrough time and the lower the
average water content in the outlet, the better is the sorption
performance. The diameter of the ethanol molecule, which
is 4.46 Å (Westgate and Ladisch, 1993), is the main deter-
mining factor of the performance of all types of molecular
sieve. Since the size of the ethanol molecule is less than the
pore diameter of type 5A molecular sieves, ethanol
molecules can pass the pores of the molecular sieves and
be sorbed there. However, as the diameter of the water
molecule is 2.8 Å (Trent, 1993), which is less than any of the
three types of molecular sieve used in this work, the three
types of the molecular sieve can easily sorb water mole-
cules. The higher adsorption capacity of type 3A molecular
sieves can be attributed to its high surface area compared to
that of type 4A and type 5A molecular sieves (Sowerby and
Crittenden, 1988).
It was expected that when molecular sieves were exposed
to more water vapour, the breakthrough time would be
shorter and the average outlet water content would
be higher. This was verified by the results of Table 1. This
can be related to the fact that as the water content is
increased in the feed, the amount of vapour that passes
through the bed will be higher, thus more water molecules
will pass through the pores. For example, for type 3A
molecular sieves, the breakthrough time was shortened
from 88.9 to 61.2 minutes when the water content was
increased from 5 to 12 wt%. Moreover, the average water
content in the condensate increased to 2.01 mol l1 at
12 wt%, which is about three times larger than the average
water content of condensate when using 5 wt% inlet water
content.
858 S. AL-ASHEH et al.

Figure 2. Breakthrough curves for ethanol–water system during water sorption on different types of molecular sieve using (A) 5 wt%; (B) 8 wt%; (C) 10 wt%;
and (D) 12 wt% inlet water content.

The main conclusion of these results is that the best
type of molecular sieve that can be used for drying of
ethanol–water mixtures type 3A. Therefore, the perfor-
mance of type 3A was considered as a datum to which the
performance of the examined biobased adsorbents was
compared.
Breakthrough Curves Using Biobased Adsorbents
Three types of biobased adsorbents were utilized for the
drying of ethanol–water mixtures using four different initial
water contents. These biobased adsorbents were: palm stone,
oak (with and without activation) and natural corncobs.
The breakthrough curves of these biobased adsorbents are
illustrated in Figure 3 using water contents of 5, 8, 10,
and 12 wt%, respectively. The shape of the breakthrough
curves obtained for these biobased adsorbents was similar
to those obtained when type A molecular sieves were used
(Figure 3).
It can be seen that the time needed to reach a plateau
value using the biobased adsorbents is shorter than that for
the molecular sieves (Figure 3). This can be attributed to
the uniform and non-uniform structures of the molecular
sieves and the biobased adsorbents, respectively. As such,
there is a possibility of ethanol being sorbed on the biobased
adsorbents. Lee et al. (1991) studied the sorption pheno-

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
 SEPARATION OF ETHANOL–WATER MIXTURES USING MOLECULAR SIEVES 859
Table 1. Breakthrough time and average outlet water content for the
sorption of water vapour on different types of molecular sieve at different
performances of the adsorbents examined in this work for
inlet water contents of an ethanol–water system. ethanol drying have the following order: type 3A > type
4A > natural palm stone > natural corncobs > activated
Average outlet palm stone > natural oak > type 5A > activated oak. This
Water content Molecular Breakthrough water content performance is judged on the basis of the breakthrough
(wt%) sieves time (min) (mol l1)
time. The average outlet water concentration, when type
5 Type 3A 88.9 0.81 5A molecular sieves were used, was higher than that of the
Type 4A 78.6 0.97 other adsorbents. Most likely, this behaviour occurred
Type 5A 49.1 1.51
8 Type 3A 81.0 1.04 because ethanol molecules might penetrate the type 5A
Type 4A 65.1 1.31 pores and be sorbed. Figure 4 compares the breakthrough
Type 5A 23.6 2.56 behaviour of molecular sieves (type 3A, type 4A, and type
10 Type 3A 67.7 1.57 5A) to that of palm stone using 5 wt% initial water content;
Type 4A 50.4 2.41
Type 5A 19.7 3.33
similar trends can be seen at other inlet water contents. This
12 Type 3A 61.2 2.07 figure verifies the facts discussed above.
Type 4A 43.1 3.05
Type 5A 12.6 4.13
Isotherms for Water Sorption on Molecular Sieves
Calculation of partial equilibrium of water vapour intro-
mena of ethanol and water on starch, which is the main duced to the fixed bed and the water uptake on the adsorbent
constituent of the biobased adsorbents, and found that at each inlet water content allows determination of isotherms
ethanol sorption can be assumed to be negligible compared for such results. There are many isotherm models that can be
to water sorption by the starchy material. This assumption applied for the results of water sorption. The Brunauer,
can also be applied to the results of this work. Emmett, and Teller (BET), a two-parameter isotherm and
The breakthrough time and the outlet average water the Guggenheim, Anderson, and de Boer (GAB), a three-
content are reported in Table 2. The water concentration parameter isotherm are the most applied models. Mathema-
for each outlet-collected sample was determined from the tically, the more parameters in a model, the better the fitting
knowledge of concentration and volume of samples collected of the experimental data. The GAB isotherm covers a wider
at different time intervals. The average concentration of all range of water activity up to 0.9, while the BET isotherm
outlet-collected samples, Cw,avg., was then calculated using covers up to 0.4 of water activity (Timmermann et al., 2001).
the following expression: Therefore, the GAB isotherm has been recommended as
Pn the fundamental equation for the characterization of water
i¼1 Vi Cw,i
Cw,avg: ¼ P n (1) sorption onto different materials (Timmermann et al., 2001).
i¼1 Vi The GAB model can be written as:
where Cw,i is the water concentration in ith sample (mol l1),
Xm CKaw
Vi is the volume of the ith sample (ml), and n is the number of X ¼ (2)
outlet-collected samples. The data of Table 2 can be used to [(1  Kaw )(1 þ (C  1)Kaw )]
compare the performance of the biobased adsorbents to that
of the molecular sieves. It is obvious that natural palm stone, Where X is water uptake on adsorbent (g H2O g1), aw is
among the tested biobased adsorbents, is the best one for water activity, Xm is the monolayer capacity (g H2O g1), C
ethanol drying; it showed the lowest average exit water is an energy constant which is related to the difference
content and the longest breakthrough time compared to the between the chemical potential of sorbate in the upper layers
other tested materials. This is true for all inlet water contents and that in the monolayer, K is also another energy constant
(Table 2). This would indicate that the surface-active func- related to the difference in the sorbate’s liquid states and
tional groups in palm stone, which are believed to be poly- the upper states (Timmermann et al., 2001).
saccharides, are more numerous than those in the other To calculate water uptake at every feed composition,
biobased adsorbents. It is also worthy mentioning that acti- which changes with time, it is necessary to know the con-
vation of palm stone and oak did not improve their sorption densate as well as the feed compositions. From the differ-
performance. On the contrary, sorption performance of these ence between the number of moles of water in the feed flask
biobased materials deteriorated upon activation (Table 2). and the number of moles of water in the condensate stream
Activation was expected to change the structure of palm the uptake of water can be calculated at each value of feed
stone and oak, so as to make them more porous materials, composition (Ladisch et al., 1984). The calculation proce-
meaning that there would be more possibility of water dure was as follows. Knowing the initial feed composition
molecules being sorbed. However, this is not the case here. allows the determination of vapour composition fed to the
It might happen that the sorption process of water within the adsorption column from the equilibrium relationship:
biobased adsorbents is determined by chemisorption.
The data of biobased adsorbents (Table 2) and that xw gw Pwsat
yw ¼ (3)
of molecular sieves (Table 1) showed that the biobased P
adsorbents have a better performance toward water sorption
than that of type 5A molecular sieves. For example, the where Pw is the partial equilibrium pressure of water, Pwsat is
breakthrough time of type 5A molecular sieves at 8 wt% is the saturation pressure of water at the isotherm temperature,
23.6 minutes, which is lower than that of all biobased xw is the water feed mole fraction, and gw is the activity
adsorbents at 8 wt%, except for activated oak. Thus, the coefficient of water that was calculated from Wilson’s

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
860 S. AL-ASHEH et al.

Figure 3. Breakthrough curves for ethanol–water system during water sorption on different biobased adsorbents using (A) 5; (B) 8; (C) 10; and (D) 12 wt%
inlet water content.

activity coefficient model. The saturation pressure was
calculated using the Antoine equation:
B the amount of ethanol collected in the first outlet sample
ln Psat ¼ A  (4)
T C
where A, B, and C are constants. The values of these
constants for water vapour are 16.29, 3816.44, and 46.13
(Smith and Van Ness, 1987). The saturation pressure in this
equation is in kPa and the temperature is in Kelvin. Since yw
equals the number of moles of water in the vapour phase
divided by the number of moles of water and ethanol,
knowing the number of moles of ethanol allows the deter-
mination of the number of moles of water fed to the column.
As ethanol was assumed not to be sorbed by the sorbents,
is the same amount of ethanol that was initially introduced
to the column as vapour. Knowing the number of moles of
ethanol in the vapour phase, the number of moles of water
can thus be calculated. Since the number of moles of water
introduced to the column and in the condensate is now
known, then water adsorbed on the sorbent can be calculated
from the difference. The water uptake can simply be
calculated by dividing the mass of water adsorbed by the
mass of the sorbent in the column.

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 SEPARATION OF ETHANOL–WATER MIXTURES USING MOLECULAR SIEVES 861
Table 2. Breakthrough time and average outlet water content for the
sorption of water vapour on different biobased adsorbents at different
inlet water contents of an ethanol–water system.

Inlet water Biobased Breakthrough Average outlet

content adsorbents time (min) water content
(wt%) (mol l1)
5 Palm stone 72.6 0.90
Natural corncobs 67.9 0.95
Activated palm stone 65.8 0.99
Oak 45.8 1.31
Activated oak 39.3 1.46
8 Palm stone 53.9 1.43
Natural corncobs 46.5 1.66
Activated palm stone 39.0 1.94
Oak 28.4 2.34
Activated oak 20.7 2.58
10 Palm stone 41.1 2.31
Natural corncobs 36.5 2.51
Activated palm stone 33.5 2.68
Oak 20.1 3.10
Activated oak 16.1 3.31
12 Palm stone 35.7 3.11 Figure 4. Breakthrough curves for sorption of water from ethanol–water
Natural corncobs 25.9 3.65 mixture onto different types of molecular sieves and natural palm stone
Activated palm stone 22.9 3.82 using 5 wt% inlet water content.
Oak 16.0 4.06
Activated oak 12.4 4.32

because it is not adsorbed by such polysaccharide materials,

The new feed composition in the boiling flask can be
calculated by subtracting the moles of ethanol and water
vaporized from the moles initially present in the flask. As
such the new value of xw was calculated and the same
calculation procedure was repeated for this new value.
Water activity was calculated from
Pw
aw ¼ sat ¼ xw gw (5)
Pw
The water activity coefficient, g, was determined using
Wilson’s equation2:
ln g1 ¼  ln (x1 þ x2 L12 )


L12 L21
þ x2  (6)
x1 þ x2 L12 x2 þ x1 L21
ln g2 ¼  ln (x2 þ x1 L21 )


L12 L21
 x1  (7)
x1 þ x2 L12 x2 þ x1 L21
Where x1 and x2 are the mole fractions of the two compo-
nents forming the system; L12 and L21 are the parameters of
Wilson’s equation (Smith and Van Ness, 1987).
The partial pressure of water vapor, pw, was calculated
using the equation of state (Smith and Van Ness, 1987):
N ZRT
pw ¼ w (8)
eV
Where Nw represents the moles of water vapor introduced to
the adsorber, Z is the compressibility factor, R is the
universal gas constant, T is the absolute temperature (K), e
is the void fraction, and V is the total volume of the adsorber
(m3). The void fraction was calculated from simple mass
balance based on knowing the weight of the bed packed
with the material alone and the weight of the same bed
packed with the same amount of material and filled with
ethanol. The difference in weight was used to calculate the
void volume. Ethanol was selected as a filling material
as mentioned earlier. The values of the compressibility
factor, Z, were determined using the method adopted by
Smith and Van Ness (1987) which is based on the critical
properties of the binary system and the Virial equation of
state. The Z values were found in the range of 0.92 to 0.95
for the ethanol–water and system.
The isotherms of water sorption on type 3A and type 4A
molecular sieves are shown in Figure 5 using 5, 8, 10, and
12 wt% inlet water contents of ethanol–water mixture. The
parameters of the GAB model were predicted by using
nonlinear regression software (Curve Expert 1.3, version
seven) produced by Daniel Hyams (2001). The predicted
data by the GAB model were compared with the experi-
mental data using the following expression for the sum
square of residuals:
X
n
(Xex,i  Xp,i )2
R2 ¼ (9)
i¼1
Xex,i
Where Xex,i and Xp,i are the ith experimental and predicted
values of water uptake on the adsorbent (g H2O g1 adsor-
bent), respectively; and n is the number of data points for
each curve. Table 3 displays the predicted parameters of the
GAB model for the different types of molecular sieve inlet
water contents.
The monolayer capacity, Xm, can be used to determine the
sorbent’s surface area at which water is adsorbed. This can
be calculated using the following equation (Neuman et al.,
1986):
Xm
surface area ¼ (N )(S:A:)w (10)
Mwt,w avog
Where Mwt,w is the molecular weight of water (g mole1),
Navog is the Avogadro’s number, and (S.A.)w is the cross
sectional area of a water molecule. The cross sectional area
of a water molecule was reported to be 1.06  1019 square
meter (Iglesias and Bueno, 1999). Calculations of the
surface area are shown in Table 3.

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862 S. AL-ASHEH et al.

It was observed that the temperatures of the feed solution

Figure 5. GAB isotherms of water sorption on (A) type 3A molecular sieves
and (B) type 4A molecular sieves at different inlet water content for
ethanol–water system. Symbols are experimental data and solid lines are
predicted by GAB model.
increased by three degrees as the inlet water content
increased from 5 to 12 wt%. The temperature at 5 wt%
inlet water content was 82
C and increased to 85
C at the
12 wt% inlet water content for the two types of molecular
sieve. This is expected since the water concentration in the
feed solutions increased, increasing the boiling temperature
of the feed solutions. Consequently, water content in the
vapour increases with the increase in the inlet water content.
Thus, it is expected that the water uptake of molecular sieves
increases as the inlet water content increases. This is more
pronounced when a certain value of water activity is taken
and the water uptake is recorded at different inlet water
content. For example, the case of water sorption on type 3A
molecular sieves (Figure 5A), at water activity of 0.1, the
water uptake was 0.11, 0.13, 0.16, and 0.17 g H2O g1
adsorbent at 5, 8, 10, and 12 wt%, respectively. This
would lead to an increase in the monolayer capacity of the
adsorbent. Theoretically, monolayer capacity (Xm) is
constant for each type of sorbent regardless of the feed
water content; however, it happens sometimes that signifi-
cant change in the monolayer capacity is noticed with the
feed water content as a result of curve fitting as noted in
Table 3. This has been amplified in the calculation of surface
area from Equation 10.
The other two GAB parameters are the energy constants.
The GAB constant, C, is related to the difference of energies
in the upper layers and that in the monolayer, while the
constant K is related to the difference of energies in the
sorbate’s pure liquid state and that in the upper layers
(Ladisch et al., 1984). Large magnitude values of the
parameter C indicate high values for heat of adsorption
(Iglesias and Bueno, 1999). This is useful for the regenera-
tion process of adsorbents. According to the values of C
calculated, it is evident that the energy constant is tempera-
ture dependent. The trend of this dependence is not so
obvious. For the type 3A molecular sieves, the constant C
increased three times as the temperature increased three
degrees only. However, for the type 4A molecular sieves,
the value of the constant C has a maximum value at the
10 wt% inlet water content and then decreases as tempera-
ture increases. However, at the same inlet water content,
the constant C in the case of type 3A molecular sieves is
always higher than that for type 4A molecular sieves. This
is due to the higher water sorption capacity of type 3A
molecular sieves than that of type 4A molecular sieves.

Table 3. The GAB parameters and surface area for water vapour sorption on different types of molecular sieve using different inlet water contents of an
ethanol–water mixture.

Water Monolayer capacity, Surface area of

Molecular Temperature content Xm (g H2O g1 Energy Energy Residuals, adsorbent (m2 g1
sieves (
C) (wt%) adsorbent) constant, C constant, K R2 adsorbent)
Type 3A 82 5 0.127 421 0.320 0.012 450
83 8 0.182 600 0.056 0.077 645
84 10 0.185 875 0.092 0.013 656
85 12 0.230 1396 0.017 0.065 815
Type 4A 82 5 0.120 380 0.135 0.055 425
83 8 0.170 519 0.032 0.073 603
84 10 0.174 584 0.030 0.048 617
85 12 0.205 304 0.035 0.064 727

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
 SEPARATION OF ETHANOL–WATER MIXTURES USING MOLECULAR SIEVES 863

Therefore, the heat of adsorption for type 3A molecular

sieves is expected to be higher than that of type 4A
molecular sieves.
Figure 5 showed that there is a sharp increase in water
uptake at low values of water activity. As elucidated in
Figure 5, at the 5 wt% inlet water content, the increase in
water uptake at low values of water activity is sharper and
more obvious than that at the other inlet water contents. This
can be related to the fact that heat of adsorption of water on
molecular sieves at the 5 wt% inlet water content is higher
than that at the other water contents; the values of the
parameter C is the highest for this water content. This
heat would cause a rise in temperature in the column and
thus enhance the adsorption process.
Teo and Ruthven (1986) studied the performance of water
sorption from aqueous ethanol solutions using type 3A
molecular sieves. They found that the maximum value of
water uptake was in the range of 0.13 to 0.16 g H2O g1
adsorbent when the water concentrations in the feed solution
was in the range of 1.3–7.3 wt%, respectively. These values
are closer to those of type 4A molecular sieves obtained in
Figure 6. GAB isotherms of water sorption on natural palm stone at
this work. However, Trent (1993) reported that the water different inlet water content of ethanol–water system.
capacity on type 3A would reach a maximum value of 0.2 g
H2O g1 adsorbent, which is much closer to those of type
3A molecular sieves obtained in this work. showed a similar trend. The parameters of the GAB model
as well as surface areas were calculated, as previously
mentioned, and are displayed in Table 4.
It can be seen (Table 4) that the values of surface area at
Isotherms for Water Sorption on
the 10 wt% are the highest compared to that at other inlet
Biobased Adsorbents
water contents. The vapour–liquid equilibrium curve of the
As was done with water sorption on molecular sieves, the ethanol–water system expands further at the10 wt% water
GAB model was used to represent the experimental results content, which results in a higher volatility than at the 8 wt%
of partial equilibrium pressure and the water uptake on and the 12 wt% water contents. This in turn increases the
the considered biobased adsorbents. The isotherms of water water vapour that is introduced to the bed when using
sorption at different inlet water contents using natural palm 10 wt% compared to that of other inlet water contents.
stone are shown in Figure 6. Isotherms for other biobased This would also be the reason for the larger surface area
adsorbents, natural corncobs, activated palm stone, oak, and of adsorbents at the12 wt% inlet water content compared to
activated oak, were also obtained (data not shown) and that of the 8 wt%.

Table 4. The GAB parameters and surface area for water vapour sorption on different biobased adsorbents at different inlet water contents for an ethanol–
water system.

Water Monolayer capacity, Surface area of

Biobased Temperature content Xm (g H2O g1 Energy Energy Residuals, adsorbent (m2 g1
adsorbents (
C) (wt%) adsorbent) constant, C constant, K R2 adsorbent)
Palm stone 80 5 0.104 350 0.053 0.05 369
81 8 0.127 693 0.033 0.08 450
82 10 0.142 263 0.04 0.02 503
83 12 0.130 275 0.025 0.10 461
Natural 80 5 0.099 529 0.034 0.10 350
corncobs 81 8 0.113 494 0.036 0.10 402
82 10 0.134 359 0.024 0.10 467
83 12 0.115 227 0.036 0.08 405
Activated 80 5 0.148 347 0.046 0.01 525
palm stone 81 8 0.150 246 0.033 0.08 532
82 10 0.187 194 0.033 0.08 663
83 12 0.158 121 0.064 0.05 560
Oak 80 5 0.087 41 0.276 0.04 308
81 8 0.096 52 0.158 0.02 340
82 10 0.118 29 0.17 0.02 418
83 12 0.105 19 0.269 0.02 372
Activated oak 80 5 0.113 60 0.174 0.07 401
81 8 0.117 34 0.198 0.02 415
82 10 0.154 39 0.121 0.02 546
83 12 0.131 32 0.152 0.01 464

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
864 S. AL-ASHEH et al.
It can also be noted that the surface area of activated
biobased adsorbents is higher than that of natural biobased
adsorbent (Table 4). For example, when using 10 wt% inlet
water content, the surface areas of activated palm stone and
that of natural are 663 and 503 m2 g1 adsorbent, respec-
tively. This is due to the fact that activation makes the
biobased adsorbents more porous. In addition, the monolayer
capacity of activated biobased adsorbents is higher than that
of natural biobased adsorbents. Therefore, the sorbents can
be ordered according to the surface area and the monolayer
capacity as follows: type 3A > type 4A > activated palm
stone > natural palm stone > activated oak > natural corn-
cobs > natural oak. This order may lead to the fact that
activated biobased adsorbents are useful materials for the
separation of ethanol–water mixtures. However, it should
be remembered that the breakthrough behaviour of water
sorption on activated biobased adsorbents is less efficient
than that of water sorption on natural biobased adsorbents
in terms of breakthrough time and average outlet water
content.
Corn, as a biobased adsorbent, is the most reported in
the literature. Neuman et al. (1986) reported that the surface
areas of water sorption, from a ethanol–water system, on
corn grits and on shelled corn were 170 and 263 m2 g1.
These values are much lower than those of natural corncobs
obtained in this work. However, Beery and Ladisch (2001)
reported that the surface area of the corn grits, for the
same system, could be 284 m2 g1. For the values of water
uptake, Hu and Xie (2001) found that sorption capacity
of cornmeal for water, from ethanol–water mixture, would
reach 0.115 g H2O g1 adsorbent over a temperature range
of 82–87
C, which is close to the results of natural
corncobs.
CONCLUSIONS
Experimental results of water sorption on molecular
sieves and biobased adsorbents showed that adsorptive
distillation could be used for separation of an ethanol–
water system. The breakthrough results of water sorption
on molecular sieves showed that type 3A molecular sieves
gave good results in terms of breakthrough time and average
outlet water concentration compared to those of type 4A and
type 5A molecular sieves. Among the biobased adsorbents
developed in this work, natural palm stone showed good
results compared to those of other biobased adsorbents.
Other biobased adsorbents gave better results in terms of
breakthrough time and average outlet water concentration
when compared to that of type 5A molecular sieves, except
for activated oak.
The GAB model reasonably represented the experimental
results of water sorption isotherms. The surface area of
type 3A molecular sieves was the largest compared to that of
type 4A molecular sieves. Type 5A molecular sieves were
found not suitable for separating an ethanol–water system
due to the possible sorption of ethanol molecules. Among
the biobased adsorbents, activated palm stone has the largest
surface area. Although activation of biobased adsorbents
resulted in an increase in the surface areas, but this did not
enhance the sorption performance for the ethanol–water
system.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A7): 855–864
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