Chemical Engineering Journal 259 (2015) 232242

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Chemical Engineering Journal

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Experimental studies on 3A and 4A zeolite molecular sieves regeneration

in TSA process: Aliphatic alcohols dewateringwater desorption
_
Gabrus a,, Jzef Nastaj a, Piotr Tabero b, Tomasz Aleksandrzak a
Elzbieta
a
b

Department of Chemical Engineering and Environmental Protection Processes, West Pomeranian University of Technology, Szczecin, Poland
Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, Szczecin, Poland

h i g h l i g h t s
 Investigations of zeolites xed bed regeneration in TSA process.
 The process parameters ensuring the most efcient zeolite xed bed regeneration.
 Adsorption equilibrium of water on zeolite 3A at high temperatures.
 Thermal stability and capacity studies of loaded zeolites.

a r t i c l e

i n f o

Article history:
Received 28 May 2014
Received in revised form 24 July 2014
Accepted 26 July 2014
Available online 4 August 2014
Keywords:
Zeolites
TSA
Alcohols dewatering
Water desorption
Isotherms
Thermal analysis

a b s t r a c t
The objective of this work are in-depth experimental studies of the thermal regeneration of the zeolite
molecular sieves 3A and 4A used to dewatering of aliphatic alcohols: ethanol, n-propanol and n-butanol.
The experimental results of water desorption during regeneration stage of temperature swing adsorption
(TSA) process, following the dewatering stage of alcohols on adsorbent xed bed contained in column are
presented. Multitemperature Langmuir-Freundlich and dual-site Langmuir-Langmuir equilibrium
models were used to correlate experimental equilibrium data of water adsorption from gas phase on
3A zeolite at temperatures 100250 C. The thermal stability, water adsorption capacity, adsorption
selectivity and thermal desorption efciency of zeolites were studied using DTA-TGA, XRD, IR and
UVVis-NIR methods. DTA-TGA investigations, carried out in the range of temperature 201000 C
revealed that water removing from 3A zeolite molecular sieve takes place up to 400 C and from 4A up
to 500 C. However, in temperatures higher than 240 C (3A zeolite) and 230 C (4A zeolite) decrease
of the water desorption rate was observed. Investigated zeolites reveal structural stability up to at least
500 C, and heating above this temperature lead to an irreversible collapse of structure and a loss of
adsorptive capacity. The inuence of the inlet purge air temperature (200250 C), and air mass ux density (0.1700.306 kg/m2s) on the zeolite dynamic water adsorption capacity, desorption and cooling steps
duration, were studied. The lowest purge air and energy consumption were measured for regeneration
temperature of 250 C. Dynamic adsorption equals to 65% of the equilibrium adsorption capacity.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, there is growing concern over the depletion of fossil
resources so a renewed interest is noted in biofuels due to energy
security and environmental pollution issues. Alternative sources of
chemicals like alcohols are gaining increasing interest as potential
substitutes for fossil sources because they can be produced by the
fermentation of renewable feedstocks [13].
In recent years the intense research concerning biofuels production takes places because of metabolic engineering progress which

Corresponding author.
http://dx.doi.org/10.1016/j.cej.2014.07.108
1385-8947/ 2014 Elsevier B.V. All rights reserved.

provides a means for fermentation improvements. The dynamic

growth of the interest in the biofuel production, especially ABE
(acetone-butanol-ethanol) process is observed. Biobutanol, produced this method can be competitive with the bioethanol according to its similar properties to that of gasoline. Well known, ABE
process is currently developed using metabolic engineering which
introduces, among others, advanced fermentation techniques e.g.
new generation of microbes and feedstock [48].
In mentioned above fermentation methods of the bioalcohols
production the concentration of the alcohols in the fermentation
broth equals typically 1020 g/L [9]. In that case, the necessity of
alcohols separation and recovery from dilute solutions exists.
Distillation is commonly applied for product recovery, but this pro-

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

cess is energy-consuming. Alternative recovery methods such as:

pervaporation, liquidliquid extraction, gas stripping, perstraction,
reverse osmosis, ionic liquids and adsorption are developed to
improve recovery productivity and reduce costs [817].
The rst four aliphatic alcohols (methanol, ethanol, propanol,
and butanol) are of interest as fuel as because their chemical
properties make them useful in internal combustion engines
[1,2,13]. Precondition of the aliphatic alcohols used as gasoline
additives is their purication, especially dewatering. For the use
in engine fuels, alcohols must contain less than 1% of water [18].
Dewatering can be carried out using various processes: distillation,
rectication, pervaporation, gas stripping, extraction and adsorption [3,6,8,1013].
The adsorption process can be used to selective removal of
water from ethanol, n-propanol and n-butanol, produced by
fermentation and then separated by distillation from the fermentation broth. Various adsorbents, such as: natural and synthetic zeolites, biobased desiccants, mostly composed of cellulose and starch
can be applied in this process [1923].
In chemical industry there are commonly used two cyclic
adsorption processes for purication and separation, especially in
the gas phase, namely thermal swing adsorption (TSA) [2328]
and pressure swing adsorption (PSA) [29,30]. In adsorption from
gas streams (most frequently from air) PSA method is useful for
volatile compounds separation, such as ethanol but useless for less
volatile compounds such as: n-propanol or n-butanol. For alcohols
dewatering in liquid phase, the TSA process can be applied. It
consists of dewatering stage eliminating water from liquid
water-alcohol mixture on a xed bed of zeolite molecular sieves
and next, the water desorption stage carried out in the same column using hot purge air ow.
The water adsorption capacities of the zeolite molecular sieves
are dependent on adsorption temperature. Therefore temperature
water adsorption equilibrium is demanded in the wide temperature range, which exists in the TSA process desorption step. The
literature research shows, that 3A and 4A molecular sieves have
analogous crystal structure and demonstrate similarities in
adsorptive capacity and selectivity [31,32]. According to Loughlin
[33] adsorption of water by 4A zeolite exhibits bifurcation behavior as a result of the presence in its crystal structures the two
cages of different volumes (a b cage volume of 151 3 and an a
cage volume of 775 3). The ratio of the volume of b cage and
a cage to the total cage volume is 0.162 and 0.838 respectively.
Such assumptions are used in this work both to 4A and 3A
zeolites.
Molecular sieves 3A and 4A are selected for investigations since
characteristic narrow structural pore openings (approximately
31010 m) enable only adsorption of smaller particles, like water
(2.61010 m) and exclude adsorption of particles of alcohols. In
the xed bed of the 3A or 4A molecular sieves contained in column,
the alcohol and water solution saturates the palletized adsorbent,
prepared by compressing zeolite crystallites (1 lm diameter)
and the binder [27]. Various kinds of clays are used as the binders
but their content is less than 1620% w/w [34]. The adsorbents
prepared in this way are considered as porous solids having macroand micro-pores [35]. The macropores in the binder are responsible for zeolite wetting with the liquid mixture and micropores in
zeolite for selective adsorption of water.
Even though there have been many theoretical and experimental
studies on TSA process [9,25,26,3638] little has been published
about adsorption and regeneration of the zeolite molecular sieves
beds used to adsorptive dewatering of organic liquids [24]. From
an economic point of view, the successful application of an adsorption system also depends on the potential to the adsorbent regeneration. There is therefore important to carry out zeolites regeneration
efciently. Incomplete water removal from zeolite bed entails low

233

water adsorption capacity in the subsequent adsorption step of

the TSA process.
The efciency of different regimes for regeneration of loaded
zeolite has been examined independently by two tasks within this
project. One of them concerns studies of xed bed desorption
column and the other is thermal analysis investigations i.e.
simultaneously conducted thermogravimetric analysis (TGA) and
differential thermal analysis (DTA). The simultaneously conducted
DTA-TGA measurements can provide information about physical
phenomena, such as sublimation, absorption, adsorption, desorption, phase transitions as well as thermal decomposition or oxidization of investigated samples [17,39]. These methods are useful
for determination of the temperature range for their thermal
stability as well as estimation of the rate of water desorption. Thus
thermal analysis methods are useful in the research on dehydration properties of zeolite molecular sieves. Infrared spectroscopy
(IR), ultravioletvisible-near infrared diffusion reectance spectroscopy (UVVis-NIR DRS) and X-ray diffraction (XRD) were also
used in the frames of this research because these measuring techniques provide valuable information on the dehydration process
and thermal stability of 3A and 4A zeolite molecular sieves as well
as on their pore structure.
Most research review concerning adsorption from liquid phase
is limited to initial laboratory evaluation of adsorption capacity in
batch experiments and no consideration is given to xed bed column studies [19,37,39,40]. There are scarce investigations which
concern dynamics of low height xed bed adsorption columns.
They usually do not include of the full cyclic TSA process research
[9,24]. In literature, the desorption stage is typically limited only to
adsorbent samples investigated through thermogravimetry
[38,41]. Pilot-plant studies and cost evaluation remain to be
explored.
In this work the innovative investigation results of the TSA process desorption stage are presented. In this stage the water loaded
xed bed of the zeolite molecular sieve (in preceding dewatering
stage) is regenerated in situ.
The aims of the here presented work are: (i) measurements of
adsorptive capacity of 3A and 4A molecular sieves at high temperatures used during their regeneration, (ii) determination of the
process parameters to ensure efcient regeneration of zeolites i.e.
high adsorption capacity, low energy and purge gas consumption,
(iii) determination of the thermal stability of the crystal structure
of 3A and 4A molecular sieves during high temperature heating,
(iv) investigation of the structural properties of zeolites capable
to selective water adsorption from water-alcohol solutions to conrm the assumption of the neglecting of the adsorption of alcohols.
2. Experimental
2.1. Materials
Technical grade (99% purity) ethanol, n-propanol and n-butanol,
were purchased from POCh, Poland S.A. Solutions of alcohols with
water were prepared separately for each adsorption run. Water
concentration in alcohols was in the range of 0.817.3 wt% for ethanol; 2.15.2 wt% for n-propanol; 3.510.4 wt% for n-butanol.
These water concentration ranges correspond with those obtained
in various stages of the alcohols purication in the fermentation
process [6,1516,1920,2325].
Molecular sieves 3A and 4A in the form of beads of approximate
diameter 1/16-in. (Sigma-Aldrich, USA) were used for studies of
adsorptive dewatering of ethanol, n-propanol and n-butanol. Basic
physical properties of zeolite 3A adsorbent are: equivalent particle
diameter 2.67 mm, bulk density 848 kg/m3; bed porosity 0.372;
particle porosity 0.662. For the zeolite 4A adsorbent, these
properties are following: equivalent particle diameter 2.67 mm,

234

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

bulk density 770 kg/m3; bed porosity 0.379; particle porosity 0.615
[42].
2.2. Analysis and measurements
During the regeneration experiment, the concentration of water
and alcohol at the exit of the bed was monitored using the gas
chromatograph equipped with a thermal conductivity detector
(TCD). Stainless steel column length 1 m, inside diameter
2.1 mm, packed with Chromosorb 101 mesh 60/80, was applied.
Column ow rate of the carrier gas (helium) was 20 cc/min in
20 C. TCD temperature was 170 C.
2.3. Adsorption isotherms
The measurements of adsorption isotherms were carried out
using the Intelligent Gravimetric Analyzer system IGA-002 (Hiden
Isochema, UK). An adsorbent sample was put in a stainless steel
container, which was suspended to the balance. Sample mass
was approximately 80 mg. The sample was placed in thermostated
reactor, which allowed achieving ultra-high vacuum. The IGA system basing on values of pressure inside the chamber automatically
controlled the input and output valves in order to achieve the set
point of pressure. After reaching equilibrium of the mass value,
the IGA system passed to the next point of isotherm (next the set
point of pressure). The isotherms were measured in temperatures
of 100, 140, 180, 200, 230, 250 C and pressures up to 11.2 kPa.
Details of the system IGA is described in our previous work [43].
2.4. Thermal analysis
Just before DTA-TGA, XRD, IR and UVVis-NIR measurements
3A and 4A adsorbents in the form of beads were ground in an agate
mortar. Samples obtained after water adsorption process prior to
grinding were additionally dried with the help of blotting paper.
Differential thermal analysis (DTA) and thermogravimetric
analysis (TGA) measurements were conducted simultaneously
using the same sample (DTA-TGA). The DTA-TGA investigations
of zeolite molecular sieves were conducted in air. Samples of mass
of 500 mg were investigated in quartz crucibles, at a heating rate of
10 C/min and in the temperature range of 201000 C. The measurements were performed using an apparatus of Paulik Paulik
Erdey type (MOM Budapest, Hungary).

(Fig. 1). In a continuous process alcohols dewatering (liquid phase)

takes place in column 1 (solution ow from the column bottom),
while TSA regeneration step (gas phase) in column 2 (hot air ow
from the column top). The stage of the alcohols dewatering (liquid
phase) is continued until zeolite molecular sieve bed breakthrough.
Then the columns are interchanged: alcohols dewatering (liquid
phase) takes place in column 2, while TSA regeneration step (gas
phase) is performed in the column 1.
The full operation stage of the alcohol dewatering (adsorption)
from alcohol-water solution in the column consist of the following
steps: water adsorption from water-alcohol solution onto zeolite
molecular sieves xed bed and gravitational draining of the
water-alcohol solution. The full operation stage of the zeolite
molecular sieve regeneration in the column consists of following
steps: thermal desorption of zeolite molecular sieves, using ow
of a hot air stream through the xed bed and cooling of the zeolite
xed bed using cold air. The cooling step was continued until the
adsorption temperature (about 30 C) was reached.
A xed bed experimental apparatus in a laboratory scale is used
to investigate alcohols dewatering from liquid water-alcohol solution using zeolite molecular sieves 3A or 4A and then zeolites
regeneration in TSA process [44]. The column diameter is 50 mm,
height 760 mm, lled with zeolite molecular sieves 3A (1.297 kg)
or 4A (1.130 kg). The column is insulated with a 0.05 m mineral
wool jacket.
In the laboratory measurements, the runs were conducted to
adsorbent bed saturation to obtain the full breakthrough curves.
The experimental investigations and modeling of the dewatering
stage is described in details in our earlier work [42].
TSA regeneration step (gas phase) in the column is performed
using hot air stream at constant temperature in the range from
200 C to 250 C. The vapor of water-alcohol mixture is condensed,
weighted and its composition is analyzed by a chromatographic
method. The direction of the hot air stream ow (during the TSA
regeneration step) is countercurrent to the liquid mixture
(water-alcohol) ow in the dewatering step (Fig. 1). Thermal

dry air
heater

2.5. X-ray diffraction (XRD)

Col.1
The powder diffraction patterns of molecular sieve samples
were recorded with the diffractometer DRON-3 (Bourevestnik,
Sankt Petersburg, Russia) using the radiation CoKa/Fe (angular
range 1252 2H, step = 0.02 2H, time t = 1 s).

Col.2
air
dewatered alcohol

2.6. Spectroscopic measurements

The IR measurements were conducted at room temperature in
the wave-number range of 4000250 cm1 using the spectrometer
Specord M80, (Carl Zeiss, Jena, Germany). A technique of pressing
pellets with KBr at a mass ratio of 1:300 was applied. The
UVVis-NIR, DRS measurements were conducted using spectrophotometer of V-670 type matched with integrating sphere
PIN-757 (JASCO, Japan) in the wavelength range of 1902150 nm.
2.7. Dewatering of liquid alcohols and regeneration of zeolites in
column
Investigated cyclic process: alcohols dewatering (liquid phase)
- TSA regeneration step (gas phase) was carried out in two columns

Col.3
vapors
condenser/ separator
alcohol+water
solution

water+alcohol
condensate

Fig. 1. Scheme of continuous TSA process: aliphatic alcohols dewatering stage

(solid line) xed bed regeneration stage (dot line); Col. 1, Col. 2 xed bed of
zeolite molecular sieves, Col. 3 environment protection column.

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

desorption step ended when the mass increase of the condensate

was not observed. Next, the xed bed of zeolite molecular sieve
is cooled using cold air owing through the bed.
These investigations were carried out for three aliphatic alcohols containing various amount of water in alcohol at the column
inlet. The selected operating conditions of the laboratory measurements are presented in Table 3. The concentration curves and temperature proles are obtained as results of the measurements.
3. Results and discussion
3.1. Effect of temperature on zeolite adsorption capacity and
determination of thermodynamic parameters
Temperature is a signicant parameter affecting both adsorption capacity of zeolite adsorbents and adsorption process kinetics.
The adsorption isotherms for water vapor on zeolite 3A belong to
type I of the BDDT classication [45,46].
The Langmuir-Freundlich model is correlated with multitemperature adsorption equilibrium data:

q qs

b  pn
1 b  pn

qs a0

a1
a2

T 273 T 2732

b exp b0

n n0

b1
b2

T 273 T 2732

1a

measure of tting accuracy is calculated as the average relative

error d (%):




N 
1X
qexpi  qcalci 
d
  100


N i1 
qexpi

where N is the number of experimental points, qexp is the experimental adsorption capacity, and qcalc is calculated adsorption capacity from the regression equation.
The t of the multitemperature Langmuir-Freundlich model to
the equilibrium data is presented in Table 1. It is evident that an
average relative error of approximation is 11.22%. Experimental
and calculated from Langmuir-Freundlich model isotherms of
water vapor on zeolite 3A at various temperatures are presented
in Fig. 2.
The t of the dual-site model of Langmuir-Langmuir to the
equilibrium data is presented in Table 2. It is evident that an average relative error of approximation is in the range from 4.69% for
100 C to 17.06% for 250 C.
The both equilibrium models can be used in mathematical modeling of the zeolite molecular sieve regeneration stage in TSA column process. The rst, multitemperature Langmuir-Freundlich
model is most general, but other one, dual-site Langmuir-Langmuir
can be more useful to reect dual structure of zeolite molecular
sieves.
3.2. Adsorption thermodynamics

!
1b

a1
T 273

1c

where q is the adsorbed phase (water) concentration (mol/kg), qs is

the saturated adsorbed phase concentration (mol/kg), p is the partial pressure of the adsorbate (Pa), and T is the temperature (C).
Water adsorption equilibrium on zeolite molecular sieves can
be described by a dual-site model, which reects bifurcated adsorbent structure. Based on Loughlin [33], the dual-site model of
Langmuir-Langmuir is also used. The mathematical form of the
mentioned models is:

q 0:162  qs

235

kb  p
ka  p
0:838  qs
1 kb  p
1 ka  p

where qs is the saturated adsorption capacity (mol/kg), p is the partial pressure of the adsorbate (Pa), ka is the equilibrium constant for
cage a (1/Pa), kb is the equilibrium constant for cage b (1/Pa). The
isotherm correlated parameters and the average relative errors for
Langmuir-Langmuir model is shown in Table 2.
The tted isotherm constants are obtained by nonlinear
regression estimation using least squares method according to
Levenberg-Marquard algorithm in program Statistica 10. The

Table 1
Fitted constants of Langmuir-Freundlich adsorption isotherm.
Parameters and errors

Value

a0102 (mol/kg)
a1 (1/K)
a2101 (1/K)
b0 (1/Pa)
b1102 (1/K)
b2101(1/K)
n0103 (-)
n1101(1/K)
d (%)

24.486
29.161
74.336
10.659
19.694
93.358
92.940
34.056
11.22

The enthalpy of adsorption was determined from the experimental equilibrium data at several temperatures. The isosteric heat
of water adsorption DH on zeolite 3A molecular sieves can be calculated from transformed the vant Hoff equation [47,48]:

!
D ln p
DH R
D 1T

4
q

where: R is universal gas constant, J/molK. From the adsorption

isotherms (Fig. 2) the adsorption isostere is plotted as relationship
of the ln p versus 1/T. Calculated in this way the isosteric heat
adsorption DH is 45.95 kJ/mol at constant adsorption capacity
q = 0.02 kg/kg.
3.3. Thermal analysis and structural investigations
Differential thermal analysis (DTA) and thermogravimetric
analysis (TGA) have been used to investigate adsorption capacity
of 3A and 4A zeolite molecular sieves. Fig. 3a and b shows representative DTA (top) and TGA (bottom) curves of molecular sieves
3A recorded after adsorption of water from the water-ethanol
and water-n-butanol solutions, respectively. On the basis of the
DTA-TGA research one can state that the loss of water from the
zeolite molecular sieve samples occurs in the temperature range
40400 C in the case of 3A zeolite molecular sieve and in the range
of 40500 C in the case of 4A zeolites. In the DTA curve of 3A
molecular sieves recorded after adsorption of water from the
water-ethanol mixture (Fig. 3a, top) one broad endothermic effect
is recorded up to 500 C with two weak maxima at 130 and 240 C.
On the other hand in the DTA curve for molecular sieves 3A
recorded after adsorption of water from the watern-butanol mixture (Fig. 3b, top) one broad endothermic effect is seen up to 500 C
with three maxima at 130, 230 and 315 C. In this case simultaneously recorded TGA curve is also more complex and contains
one feebly pronounced maximum at 130 C and inection at
230 C (Fig. 3b, bottom). These results are in accord with literature
data where the endothermic effects in this temperature range are
attributed to desorption of water from the sorbent [31,41,49,50].

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

236

Table 2
Fitted constants and average relative errors Langmuir-Langmuir (dual-site) equilibrium model.
Model

Parameters and errors

LangmuirLangmuir

qs102 (kg/kg)
kb103 (1/Pa)
ka103(1/Pa)
d (%)

Temperature
100 (C)

140 (C)

180 (C)

200 (C)

230 (C)

250 (C)

15.459
4.766
1.512
4.685

15.915
5.736
0.271
6.725

11.757
2.292
0.180
14.681

7.482
2.862
0.209
14.162

4.585
0.856
0.531
16.315

3.875
0.834
0.669
17.064

Table 3
Operating conditions for adsorption (dewatering) and desorption (regeneration) stages of TSA process: aliphatic alcohols dewatering zeolite molecular sieve regeneration.
Adsorption (dewatering) stage

Desorption (regeneration) stage

tads (min)

tdes (min)

mG (kg/m2s)

Tr (C)

qd (kg/kg)

RL (%)

Ethanol/water/zeolite molecular sieve 3A

E2
0.1424
2.89
E8
0.0738
0.75
E9
0.0508
3.00
E10
0.1412
2.07
E12
0.0894
1.89
E13
0.0993
2.56

125
512
320
276
277
153

310
239
234
324
176
275

0.306
0.306
0.306
0.238
0.272
0.306

250
250
250
250
240
200

0.169
0.160
0.163
0.166
0.162
0.129

3.79
1.78
0.79
2.15
2.43
1.25

n-Propanol/water/zeolite molecular sieve 3A

P2
0.021
2.93
P3
0.032
2.83
P4
0.051
1.75
P5
0.044
4.04
P7
0.034
3.07

500
340
420
240
330

290
283
358
360
300

0.272
0.306
0.238
0.306
0.272

250
250
250
250
230

0.149
0.164
0.128
0.142
0.124

1.68
2.32
1.52
2.19
1.67

n-Butanol/water/zeolite molecular sieve 4A

B1
0.044
4.00
B2
0.040
3.00
B5
0.060
2.00
B7
0.050
2.00
B8
0.035
2.00

630
600
610
640
710

380
405
570
320
340

0.238
0.204
0.170
0.306
0.272

250
250
250
250
250

0.146
0.149
0.144
0.152
0.148

1.03
0.89
0.86
0.79
0.84

Cycle no.

C0 (kg/kg)

w104 (m/s)

Fig. 2. Experimental and calculated multitemperature Langmuir-Freundlich isotherms for water vapor on zeolite molecular sieve 3A.

The initial mass loss of the samples, below 100 C, is presumably

caused by desorption of physically adsorbed water from within
the solid microstructure. One cannot exclude that at these temperatures (close to 40 C) a small amounts of alcohols adsorbed by the

surface layer of adsorbents start to desorb. Analysis of the course of

all TGA curves for 3A and 4A loaded zeolites indicates that the used
regeneration temperature (up to 250 C) enables approximately
65% water removing from 3A and 75% from 4A zeolite molecular
sieves.
To estimate the thermal stability of adsorbents, the zeolite
molecular sieves 3A and 4A before and after adsorption, after additional heating tests at 500 C and after DTA-TGA measurements up
to 1000 C have been subjected to investigations with the aid of the
XRD method. Fig. 4 shows the fragments of representative powder
diffraction patterns of 3A and 4A zeolite molecular sieves after
heating tests at 500 C (Fig. 4, curves a and b) and after DTA-TGA
measurements (Fig. 4, curves c and d). The powder diffraction patterns of all 3A and 4A molecular sieve samples, before and after
adsorption, as well as after heating tests at 500 C are similar and
also similar to the diffraction patterns of 3A and 4A zeolite molecular sieves given in literature [32]. It indicates that heating at temperatures up to 500 C does not affect the crystal structure of 3A
and 4A zeolites. It indicates on the preservation of zeolite structure
and its characteristics adsorptive properties in this temperature
range. On the other hand diffraction patterns of 3A and 4A zeolites
recorded after DTA-TGA measurements conducted up to 1000 C
differ considerably from these ones registered before DTA-TGA
measurements. Thus the results of XRD investigations (Fig. 4)
prove that regeneration temperatures over critical values, approximately 800 C [49,50], lead to an irreversible collapse of the zeolite
molecular sieve structure and a loss of adsorptive capacity. Despite
similarities in diffraction patterns of 3A and 4A zeolites recorded
after DTA-TGA measurements the angular position of diffraction
lines are shifted considerably enabling differentiation of 3A and
4A zeolites (Fig. 4, curve c and d).

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

237

to IR investigations. Fig. 5a shows the representative IR spectra

of 3A zeolite molecular sieve recorded after adsorption of water
from the solutions with ethanol, n-propanol, n-butanol and zeolite
molecular sieve 3A after DTA-TGA measurement up to 1000 C. The
IR spectra of 3A and 4A molecular sieves recorded after adsorption
of water from different alcohols are very similar (Fig. 5a). These
spectra comprise absorption bands with maxima at 1644 and
3440 cm1 which are produced by adsorbed water molecules
[17]. On the other hand, absorption bands in the range of
2501200 cm1 are characteristic for aluminosilicate groups,
building structure of zeolites [32]. It is noteworthy that IR spectra
of 3A and 4A zeolite molecular sieves recorded after adsorption of
water from alcohol-water solutions (Fig. 5a) do not include absorption bands characteristic for alcohols [20]. These bands should be
recorded in the spectra of samples in the case of adsorption of
alcohols by zeolites. The lack of these bands implies that 3A and
4A molecular sieves in the course of adsorption process do not
adsorb detectable by IR spectroscopy amounts of alcohols from
wateralcohol solutions. On the other hand IR spectra of 3A and
4A zeolite molecular sieves recorded after DTA-TGA measurements
up to 1000 C (Fig. 5a, bottom) differ considerably from the previous ones (Fig. 5a). The absorption bands characteristic for the
adsorbed water molecules have much lower intensities in these

Fig. 3. DTA (top) and TGA (bottom) curves of molecular sieves 3A recorded after
adsorption of water from water-ethanol solution (graph a) and recorded after
adsorption of water from water-n-butanol solution (graph b).

Fig. 4. The fragments of powder diffraction patterns of 3A and 4A zeolite molecular

sieves recorded after heating tests at 500 C (curves a and b) and after DTA-TGA
measurements up to 1000 C (curves c and d).

3.4. Spectroscopic measurements

The 3A and 4A zeolite molecular sieves both after adsorption
process and after DTA-TGA measurements have been subjected

Fig. 5. IR spectra (graph a) of 3A zeolite molecular sieve samples after adsorption of

water from ethanol, n-propanol, n-butanol and after DTA-TGA measurement up to
1000 C and UVVis-NIR spectra (graph b) of 3A zeolite after adsorption of water
from ethanol and after DTA-TGA measurement up to 1000 C.

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

3.5. Fixed bed column studies of zeolites regeneration

The TSA process was applied to the aliphatic alcohols dewatering, where the water adsorption step on the zeolite xed bed was
carried out from liquid alcohol solution. Next the zeolite adsorbent
regeneration step was carried out in situ using hot inert gas. After
the adsorption process the bed of adsorbent was saturated with
alcohol and water solution. Despite the fact that alcohol was not
adsorbed in the zeolite molecular sieves micropores, it was nevertheless present in macropores and in a lm around the adsorbent
particles. The experimental and modeling studies of adsorption
step (alcohol dewatering) were presented in our previous papers
[43,44]. During the desorption experiment the concentration of
water and temperatures at various positions inside the bed, were
monitored. Attention was paid to the temperature proles, and
the water and alcohol (ethanol, n-propanol or n-butanol) loading
changes on adsorbent particles during the process of desorption.
The elapsed time from the start of the desorption step to the
moment when the mass of condensate did not change, was taken
as the time of desorption tdes. The air leaving column owed to condenser and next was directed to environment protection column to
avoid emission of the alcohol vapor. The condensate was periodically weighted and chromatographically analyzed.
During desorption step the alcohol concentration in the air
stream rapidly increases in the initial period to achieve maximum
value and then decreases down to zero. It is obvious that this rollup phenomenon can be explained by the equilibrium effect caused
by temperature changes [28].
The operating conditions of selected runs of the cyclic TSA process for dewatering and regeneration stages are presented in
Table 3. The operating conditions concerning dewatering stage
are: inlet water concentration C0 and liquid apparent velocity w.
The operating conditions concerning the regeneration stage are:
air mass ux density mG, and desorption temperature Tr. The operating conditions of cooling step were the same in each cycle: air
mass ux density (0.306 kg/m2s) and air temperature (25 C).
Adsorption time tads, desorption time tdes and cooling time tcool
depend on TSA steps operating conditions. The mass of adsorbed
water in xed bed relating to total mass of zeolite adsorbent was
dened as the dynamic adsorption qd (kg/kg). The values qd, for
each adsorption-desorption cycle were determined from the complete mass balance.
The relative losses values RL (%) for selected experimental runs
are presented in the Table 3. The alcohols loss in the condenser/
separator and in air stream leaving the vapor-liquid separator
changes in the range 0.793.79% for ethanol; 1.522.32% for

n-propanol and 0.791.03% for n-butanol, according to combination of the process parameters imposed.
In the regeneration stage the total desorption time decreases
with values increasing of the operating parameters values, namely
hot air temperature and its mass ux density. The dynamic adsorption depends on operating parameters values used in the whole
TSA process both in adsorption stage and following regeneration
stage.
The cooling step duration depends on zeolite molecular sieve 3A
or 4A xed bed temperature at the end of the regeneration stage.
The cooling times (tcool) depending on the bed temperature (Tr) were
approximately as follows: tcool = 60 min for Tr = 200 C; tcool =
70 min for Tr = 210 C; tcool = 80 min for Tr = 220 C; tcool = 90 min
for Tr = 230 C; tcool = 100 min for Tr = 240 C; tcool = 120 min for
Tr = 250 C. To maintain operation continuity of the two column
installation TSA (Fig. 1) the regeneration stage duration must be
shorter or at most equal to adsorption stage duration. Based on
experimental results of the alcohols dewatering containing various
water amounts it can be stated that in the case of application of
adequate process operating conditions fullls this demand. It took
place in the cycles E8, P2, B1, B2, B7, and B8. In other cases the operation discontinuity of the TSA system (desorption step and cooling
step durations were longer than dewatering stage duration) was
observed. Use of the adequate operating process parameters
enables continuous two-column TSA installation operation.
The concentration breakthrough curves at the column outlet
obtained as results of the measurements are presented in Fig. 6.
It is evident that alcohol evaporates rst followed by water. Water
desorption demand energy supply to overcome of bonding forces.
The signicance of the heat of adsorption can be seen in the
region of unsteady state proles at the four xed-bed heights
and at the outlet. Temperature measurements results at various
heights of the xed bed are presented in Fig. 7. In this gure one
can see, that in non-adiabatic conditions, temperature values
decrease along the bed height, which proves the existence of heat
losses. Energy effects can be observed on temperature curves
(Fig. 7) in the form of plateau regions, corresponding to intensive
alcohol evaporation and inection curves during water desorption.
Fig. 8 shows the temperature breakthrough curves, at h = 0.4 m
axial position, during desorption step followed adsorptive alcohols
dewatering. All curves have specic shape with plateau occurring
at temperatures characteristic for each examined system.
Four regions are observed during desorption step runs (Figs. 7
and 8). The initial section up to 40 C corresponds to the liquid

70
60
3

spectra. It indicates that after heat treatment above 800 C and collapse of the zeolite molecular sieve structure, obtained in this way
samples lose their good adsorption properties.
The 3A and 4A zeolite molecular sieves both after adsorption
process and after DTA-TGA measurements have been subjected
to UVVis-NIR investigations. Fig. 5b shows the representative
UVVis-NIR spectra of 3A zeolite molecular sieve after adsorption
of water from the water-ethanol mixture (Fig. 5b, bottom) and
after DTATGA measurement up to 1000 C (Fig. 5b, top). The
UVVis-NIR spectra of 3A and 4A molecular sieves recorded after
adsorption of water from different alcohol-water solutions are very
similar and contain absorption bands ascribed to overtones and
combination vibrations of water molecules (1430 and 1940 nm)
[51]. These spectra do not comprise absorption bands characteristic for ethanol and other alcohols [52]. It implies that 3A and 4A
molecular sieves do not adsorb considerable amounts of alcohols
and again supports our assumption concerning selective adsorption of water from water-alcohol solutions by 3A and 4A zeolites.

concentration (g/m )

238

water
ethanol

50
40
30
20
10
0
0

50

100

150
time (min)

20 0

250

300

Fig. 6. Typical concentration breakthrough curves of ethanol and water vapors at

column outlet during TSA desorption step of cyclic process (run E2).

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

T1 - 0.10 m
T2 - 0.20 m
T3 - 0.40 m
T4 - 0.60 m
T5 - 0.75 m
T6 - inlet

250

Temperature ( C)

200

150

100

50

0
0

50

100

150

200

250

300

350

239

cycles are presented in Table 3, while Fig. 9 displays the values qd

for zeolite molecular sieve 3A used for ethanol dewatering (cycles
1 through 9, and 17 through 28) and for n-propanol dewatering
(cycles 10 through 16), and for zeolite molecular sieve 4A used
for n-butanol dewatering.
The experimental results indicate that the value of the average
dynamic adsorption of 68% for molecular sieve 3A (0.1549 kg/kg)
and 62% for molecular sieve 4A (0.1497 kg/kg) of the equilibrium
adsorption value can be attained using adequate process parameters (regeneration temperature and air mass ux density). Inuence of the cycle number on the adsorbent loading is presented
in Fig. 9. The increase of adsorption loading in the initial cycles is
observed in comparison with the average values. The values of zeolites loadings in the following cycles oscillate around the average
ones.

Time (min)
Fig. 7. Typical xed bed temperature breakthrough curves at various column
positions during TSA desorption and cooling steps of cyclic process (run E2).

220
200
180

140

120
n-butanol

100

By the choice of the cycle conditions, the heat of adsorption can

be stored in a specic manner that is that heat is retained in the
bed before or after breakthrough of the water. The solid zeolite
could be integrated at a sufciently high temperature to the regeneration of the bed immediately following the adsorption step. Temperature increase in the adsorbent bed at the end of the water
adsorption step is due to the heat of adsorption release. It follows
that the endothermic water desorption step in the gas phase is
favored when temperature increases. The temperature of the
adsorbent at the end of the adsorption step may be determined
in relation to the feed temperature [53]:

ethanol

80

n-propanol

60
40
20
0
0

20

40

60

80 100 120 140 160 180 200 220 240

Time (min)

Fig. 8. Temperature proles during regeneration of zeolite molecular sieves bed

used to dewatering alcohols (runs E12, P2, B8, measured inside bed h = 0.4 m,
mG = 0.272 kg/m2s, Tr = 250 C).

evaporation and visible plateau. Then the temperature curve has

steep shape and its slope decreases above temperature of 100 C.
It is probably linked with the beginning of water desorption, after
reaching of the water boiling point. Furthermore, after attaining
the xed bed temperature of 130 C, the inection point appears.
Then, the xed bed temperature increases to about 200 C
(depending on operating conditions) and remains at the constant
level. It is probably caused by water release from the b cage. The
course of desorption curve fully corresponds with TGA investigation results, revealing the mass loss at the same temperature.
From experimental investigations it results that water adsorption capacity of the zeolite xed beds decreases in subsequent
adsorption cycles to 6070% in comparison with that obtained on
fresh adsorbent bed. It is because of incomplete water desorption
in following regeneration stages in process operating conditions
imposed. The remaining water amount in the bed forms residual
adsorption.

DT 

Dq  DH
C AV

where DT represents the difference in temperature of the adsorbent

between beginning of the adsorption (dewatering stage) and
desorption (regeneration stage) steps, DH is the heat of water
adsorption, and CAV is the average heat capacity in column (including solid adsorbent and liquid loading at the end of the adsorption
step), Dq is the working water adsorptive capacity, dening the difference equilibrium loadings of water (mol/kg) corresponding to
temperature of the adsorption (dewatering) and the desorption
(regeneration) steps. The average heat capacity in column was
computed additively using mass fractions of liquid and adsorbent,
and equals CAV = 1214 J/kg K. The adsorption capacities of zeolite

0.26
zeolite 3A

0.24
Adsorption capacity (kg/kg)

Temperature ( C)

160

3.7. Heat of adsorption in two column system

zeolite 4A
av 3A (0.1549 kg/kg)

0.22

av 4A (0.1497 kg/kg)
0.2
0.18
0.16
0.14
0.12
0.1

3.6. Effect of the number of cycles on adsorption capacity

The dynamic adsorption values qd change depending on operational conditions especially in the TSA process cycles. The selected

11

13 15

17 19 21

23 25

27 29

Cycle number (-)

Fig. 9. Effect of the number of cycles performed on water adsorption capacity of
water on 3A and 4A zeolites xed bed.

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

240

molecular sieves 3A are determined from adequate adsorption

isotherms in the liquid phase at 25 C [42] and gas phase in the
range from 200 C to 250 C, respectively. Determined value of the
adsorption heat calculated using the vant Hoff relationship is
DH = 45.95 kJ/mol. Estimated, in this way, temperature increase
of the adsorbent bed DT equal from 10 C after regeneration in temperature of 200 C to 23 C in temperature of 250 C. The existing
temperature rises at the moment of xed bed breakthrough measured in experiments are higher (increase about 1535 C) than that
calculated as average temperature rises for loaded bed in column.
This phenomenon is favorable for subsequent desorption step in
the TSA process.
3.8. Effect of purge gas temperature
Effectiveness of the water desorption process from zeolites
xed bed depends on two parameters which describe the specic
hot purge air and energy consumptions. Namely, the purge air
and energy consumptions are functions of regeneration temperature Tr [28,54]. These parameters are dened in terms of purge
air and of energy consumption, both per mass of adsorbent, Np
(mol/kg zeolite/adsorbent), and Ep (J/kg zeolite/adsorbent), respectively. The denitions of the Np and Ep are:

Np

n tdes
qb V b

Ep Np C pg T r  T 0

C pg 31:15  1:357  102 T r 273 2:68  105 T r 2732

 1:168  108 T r 2733

where n is the molar air ow rate in mol/min, qb is the air bulk density in kg/m3, Vb is the bed volume in m3, Cpg is the heat capacity of
air in J/kg K, and T0 is a reference temperature (cold air temperature
was 25 C).
The purge air consumption calculated from Eq. (6) at various
regeneration times is plotted in Fig. 10 against the regeneration
temperature. The purge air consumption decreases with the
increase in regeneration temperature. A similar result has been
found by others investigators [28,54]. At temperature of 250 C
the specic gas consumption Np (kg air/kmol water) values for ethanol, n-propanol and n-butanol equal: 0.227; 0.278; 0.294,
respectively.

3
8

2.8

Np (kmol / kg adsorbent)

2.4
2.2
2

ethanol
n-propanol
n-butanol

1.8

1.6

1.4

Ep (kJ/ kg adsorbent)

2.6

1.2
1

1
0.8
190

200

210

220

230

240

250

0
260

Desorption temeprature ( C)
Fig. 10. Effect of purge air temperature on specic gas consumption Np and effect of
specic energy consumption Ep.

The energy consumption calculated from Eq. (7) at various

regeneration temperatures is presented in Fig. 10 where the purge
air temperatures which give the minimal energy consumptions for
various adsorption systems are shown. As it can be seen the minimal energy consumption for the investigated systems, appears
in temperature of about 240 C. In this temperature the specic
energy consumption Ep (kJ/kg adsorbent) values for ethanol,
n-propanol and n-butanol equal: 1.256; 1.541; 1.627, respectively.
Main operating costs in the TSA process of alcohol dewatering
take place in the regeneration stage. It results from the experimental investigations that energy consumption in TSA process is about
0.92 MJ/kg ethanol; 0.96 MJ/kg n-propanol; 1.14 MJ/kg n-butanol.
The data from literature give energy consumed using pervaporation, 0.84 MJ/kg ethanol and 2.26 MJ/kg water and simultaneously
energy requirement for azeotropic distillation is 3.31 MJ/kg ethanol [55]. The above presented data concern of the ethyl alcohol
dewatering in the concentration range of 9599.5 wt%.
3.9. Determination of the process parameters ensuring efcient zeolite
bed regeneration
The experimental investigations of both the xed bed column
desorption and loaded zeolite samples thermal analyses were
carried out. They enabled determination of process parameters
ensuring most efcient zeolite bed regeneration in the examined
variability range. With increase of imposed regeneration temperature Tr, effectiveness of zeolite bed regeneration increases what
causes also increase of the bed dynamic adsorption capacity in
the subsequent TSA cycle (adsorption step). With increase of the
imposed purge gas mass ux density shortening of desorption step
duration was observed (Table 3).
The energetic endothermic effect observed on the DTA curve in
temperature about 240 C (Fig. 3), corresponding with maximal
rate of water releasing was the one of the optimization criteria.
Above this temperature rate of the process considerably decreases
what in consequence causes increase of desorption step duration.
Analysis of the course of all TGA curves for 3A and 4A loaded
zeolites indicates that the used regeneration temperature (up to
250 C) enables approximately 65% water removing from 3A and
75% from 4A zeolite molecular sieves.
Energy consumption in the temperature range (230250 C),
determined in column investigation, is nearly constant and purge
gas consumption in this temperature range slightly decreases
(Fig. 10). Increasing of air mass ux density causes decreasing of
the desorption step duration. The XRD investigations revealed
the thermal stability of the zeolite structure what ensures long
time of zeolites bed exploitation. The zeolites regeneration process
carried out in temperature about 250 C is both effective and
simultaneously safe for adsorbent structure.
On the other hand, from the results of experimental measurements it is clear that multiply regeneration of the xed bed adsorbent does not inuence greatly the adsorbent structural changes.
The dynamic adsorption capacity is maintained on the level about
65%.
4. Conclusions
The investigations have revealed that dewatering of aliphatic
alcohols using 3A and 4A zeolite molecular sieves and their regeneration, in the TSA process, are effective at the operating conditions
determined in this study. The innovative experiments are carried
out in full TSA cycles comprising of dewatering and regeneration
stages for three water-alcohol systems that are the ethanol,
n-propanol, and n-butanol. It is evident that the regeneration stage
plays a pivotal role in this TSA process. The measurements show

E. Gabrus et al. / Chemical Engineering Journal 259 (2015) 232242

that zeolites regeneration is a multilevel process due to biporous

structure of adsorbent particles (consisted of the crystallites and
the binder) and bifurcation in structure of crystallite. In accordance
with that, the gradual water release is observed. In the rst stage
the intensive alcohol-water solution evaporation takes place (in
temperature about 40 C), mainly contained in a liquid lm of
the zeolite particles surroundings. Next, the loss of water from
the zeolite molecular sieves occurs in the temperature range of
40400 C in the case of 3A zeolite molecular sieve and
40500 C in the case of 4A. Temperature of water desorption
should be higher than 130 C, when water desorption takes place
in the bounded b cage structure and should be lower than destruction temperature of 800 C. Thermogravimetric analysis revealed
that zeolite molecular sieve heating above 240 C is not favorable
for investigated process because of decreasing of the process rate
is observed. The regeneration time, energy and purge gas consumptions depend on the operating conditions (i.e. regeneration
temperature, mass air ux density). The possible smallest air and
energy consumptions, in examined temperature range, were
received at purge gas temperature of 250 C at dynamic adsorption
of 65% equilibrium adsorption capacity. In this temperature the
specic gas consumption Np and specic energy consumption Ep
values for ethanol, n-propanol and n-butanol equal to 0.227,
1.256; 0.278, 1.541; 0.294, and 1.627, respectively. The continuous
operation of the TSA installation can be performed in two columns
using adequate operating process parameters. Furthermore, the
mathematical modeling of the regeneration stage of the TSA process should be developed in the near future.
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