Chemical Engineering Journal 259 (2015) 232–242

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

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

in TSA process: Aliphatic alcohols dewatering–water desorption
_
Elzbieta Gabruś a,⇑, Józef Nastaj a, Piotr Tabero b, Tomasz Aleksandrzak a
a
Department of Chemical Engineering and Environmental Protection Processes, West Pomeranian University of Technology, Szczecin, Poland
b
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 fixed bed regeneration in TSA process.

 The process parameters ensuring the most efficient zeolite fixed 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 a b s t r a c t

Article history: The objective of this work are in-depth experimental studies of the thermal regeneration of the zeolite
Received 28 May 2014 molecular sieves 3A and 4A used to dewatering of aliphatic alcohols: ethanol, n-propanol and n-butanol.
Received in revised form 24 July 2014 The experimental results of water desorption during regeneration stage of temperature swing adsorption
Accepted 26 July 2014
(TSA) process, following the dewatering stage of alcohols on adsorbent fixed bed contained in column are
Available online 4 August 2014
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
Keywords:
3A zeolite at temperatures 100–250 °C. The thermal stability, water adsorption capacity, adsorption
Zeolites
TSA
selectivity and thermal desorption efficiency of zeolites were studied using DTA-TGA, XRD, IR and
Alcohols dewatering UV–Vis-NIR methods. DTA-TGA investigations, carried out in the range of temperature 20–1000 °C
Water desorption revealed that water removing from 3A zeolite molecular sieve takes place up to 400 °C and from 4A up
Isotherms to 500 °C. However, in temperatures higher than 240 °C (3A zeolite) and 230 °C (4A zeolite) decrease
Thermal analysis 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 influence of the inlet purge air temperature (200–250 °C), and air mass flux den-
sity (0.170–0.306 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.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction provides a means for fermentation improvements. The dynamic

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 feedstock’s [1–3].
In recent years the intense research concerning biofuels produc-
tion takes places because of metabolic engineering progress which
⇑ Corresponding author.
growth of the interest in the biofuel production, especially ABE
(acetone-butanol-ethanol) process is observed. Biobutanol, pro-
duced this method can be competitive with the bioethanol accord-
ing 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 [4–8].
In mentioned above fermentation methods of the bioalcohols
production the concentration of the alcohols in the fermentation
broth equals typically 10–20 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-

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

Downloaded from http://www.elearnica.ir

 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242
cess is energy-consuming. Alternative recovery methods such as:
pervaporation, liquid–liquid extraction, gas stripping, perstraction,
reverse osmosis, ionic liquids and adsorption are developed to
improve recovery productivity and reduce costs [8–17].
The first 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 purification, 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,
rectification, pervaporation, gas stripping, extraction and adsorp-
tion [3,6,8,10–13].
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 fermenta-
tion broth. Various adsorbents, such as: natural and synthetic zeo-
lites, biobased desiccants, mostly composed of cellulose and starch
can be applied in this process [19–23].
In chemical industry there are commonly used two cyclic
adsorption processes for purification and separation, especially in
the gas phase, namely thermal swing adsorption (TSA) [23–28]
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 fixed bed of zeolite molecular sieves
and next, the water desorption stage carried out in the same col-
umn using hot purge air flow.
The water adsorption capacities of the zeolite molecular sieves
are dependent on adsorption temperature. Therefore temperature
water adsorption equilibrium is demanded in the wide tempera-
ture 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 behav-
ior as a result of the presence in its crystal structures the two
cages of different volumes (a b cage volume of 151 Å3 and an a
cage volume of 775 Å3). 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 fixed 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 16–20% w/w [34]. The adsorbents
prepared in this way are considered as porous solids having macro-
and micro-pores [35]. The macropores in the binder are responsi-
ble 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 [9,25,26,36–38] 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 adsorp-
tion system also depends on the potential to the adsorbent regener-
ation. There is therefore important to carry out zeolites regeneration
efficiently. Incomplete water removal from zeolite bed entails low
233
water adsorption capacity in the subsequent adsorption step of
the TSA process.
The efficiency of different regimes for regeneration of loaded
zeolite has been examined independently by two tasks within this
project. One of them concerns studies of fixed 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, desorp-
tion, phase transitions as well as thermal decomposition or oxidi-
zation 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 dehydra-
tion properties of zeolite molecular sieves. Infrared spectroscopy
(IR), ultraviolet–visible-near infrared diffusion reflectance spec-
troscopy (UV–Vis-NIR DRS) and X-ray diffraction (XRD) were also
used in the frames of this research because these measuring tech-
niques 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 fixed bed col-
umn studies [19,37,39,40]. There are scarce investigations which
concern dynamics of low height fixed 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 pro-
cess desorption stage are presented. In this stage the water loaded
fixed 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 temper-
atures used during their regeneration, (ii) determination of the
process parameters to ensure efficient 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 con-
firm 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 0.8–17.3 wt% for eth-
anol; 2.1–5.2 wt% for n-propanol; 3.5–10.4 wt% for n-butanol.
These water concentration ranges correspond with those obtained
in various stages of the alcohols purification in the fermentation
process [6,15–16,19–20,23–25].
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. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242
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 flow 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 sys-
tem 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 UV–Vis-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 20–1000 °C. The mea-
surements were performed using an apparatus of Paulik – Paulik
– Erdey type (MOM Budapest, Hungary).
2.5. X-ray diffraction (XRD)
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 12–52 °2H, step = 0.02 °2H, time t = 1 s).
2.6. Spectroscopic measurements
The IR measurements were conducted at room temperature in
the wave-number range of 4000–250 cm–1 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
UV–Vis-NIR, DRS measurements were conducted using spectro-
photometer of V-670 type matched with integrating sphere
PIN-757 (JASCO, Japan) in the wavelength range of 190–2150 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
(Fig. 1). In a continuous process alcohols dewatering (liquid phase)
takes place in column 1 (solution flow from the column bottom),
while TSA regeneration step (gas phase) in column 2 (hot air flow
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 fixed 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 flow
of a hot air stream through the fixed bed and cooling of the zeolite
fixed bed using cold air. The cooling step was continued until the
adsorption temperature (about 30 °C) was reached.
A fixed bed experimental apparatus in a laboratory scale is used
to investigate alcohols dewatering from liquid water-alcohol solu-
tion using zeolite molecular sieves 3A or 4A and then zeolites
regeneration in TSA process [44]. The column diameter is 50 mm,
height 760 mm, filled 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 flow (during the TSA
regeneration step) is countercurrent to the liquid mixture
(water-alcohol) flow in the dewatering step (Fig. 1). Thermal
dry air
heater
Col.1 Col.2
air
dewatered alcohol
Col.3
vapors
condenser/ separator
alcohol+water
solution water+alcohol
condensate
Fig. 1. Scheme of continuous TSA process: aliphatic alcohols dewatering stage
(solid line) – fixed bed regeneration stage (dot line); Col. 1, Col. 2 – fixed bed of
zeolite molecular sieves, Col. 3 – environment protection column.
 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242 235

desorption step ended when the mass increase of the condensate measure of fitting accuracy is calculated as the average relative
was not observed. Next, the fixed bed of zeolite molecular sieve error d (%):
is cooled using cold air flowing through the bed.  
N  
These investigations were carried out for three aliphatic alco- 1X qexpi  qcalci 
d¼    100 ð3Þ
hols containing various amount of water in alcohol at the column N i¼1  qexpi 
inlet. The selected operating conditions of the laboratory measure-
ments are presented in Table 3. The concentration curves and tem- where N is the number of experimental points, qexp is the experi-
perature profiles are obtained as results of the measurements. mental adsorption capacity, and qcalc is calculated adsorption capac-
ity from the regression equation.
The fit of the multitemperature Langmuir-Freundlich model to
3. Results and discussion
the equilibrium data is presented in Table 1. It is evident that an
average relative error of approximation is 11.22%. Experimental
3.1. Effect of temperature on zeolite adsorption capacity and
and calculated from Langmuir-Freundlich model isotherms of
determination of thermodynamic parameters
water vapor on zeolite 3A at various temperatures are presented
in Fig. 2.
Temperature is a significant parameter affecting both adsorp-
The fit of the dual-site model of Langmuir-Langmuir to the
tion capacity of zeolite adsorbents and adsorption process kinetics.
equilibrium data is presented in Table 2. It is evident that an aver-
The adsorption isotherms for water vapor on zeolite 3A belong to
age relative error of approximation is in the range from 4.69% for
type I of the BDDT classification [45,46].
100 °C to 17.06% for 250 °C.
The Langmuir-Freundlich model is correlated with multitem-
The both equilibrium models can be used in mathematical mod-
perature adsorption equilibrium data:
eling of the zeolite molecular sieve regeneration stage in TSA col-
b  pn umn process. The first, multitemperature Langmuir-Freundlich
q ¼ qs ð1Þ model is most general, but other one, dual-site Langmuir-Langmuir
1 þ b  pn
can be more useful to reflect dual structure of zeolite molecular
a1 a2 sieves.
qs ¼ a0 þ þ ð1aÞ
T þ 273 ðT þ 273Þ2
3.2. Adsorption thermodynamics
!
b1 b2
b ¼ exp b0 þ þ ð1bÞ The enthalpy of adsorption was determined from the experi-
T þ 273 ðT þ 273Þ2 mental equilibrium data at several temperatures. The isosteric heat
of water adsorption DH on zeolite 3A molecular sieves can be cal-
a1 culated from transformed the van’t Hoff equation [47,48]:
n ¼ n0 þ ð1cÞ
T þ 273 !
D ln p
where q is the adsorbed phase (water) concentration (mol/kg), qs is DH ¼ R ð4Þ
D 1T
the saturated adsorbed phase concentration (mol/kg), p is the par- q

tial pressure of the adsorbate (Pa), and T is the temperature (°C).

where: R is universal gas constant, J/molK. From the adsorption
Water adsorption equilibrium on zeolite molecular sieves can
isotherms (Fig. 2) the adsorption isostere is plotted as relationship
be described by a dual-site model, which reflects bifurcated adsor-
of the ln p versus 1/T. Calculated in this way the isosteric heat
bent structure. Based on Loughlin [33], the dual-site model of
adsorption DH is 45.95 kJ/mol at constant adsorption capacity
Langmuir-Langmuir is also used. The mathematical form of the
q = 0.02 kg/kg.
mentioned models is:

kb  p ka  p 3.3. Thermal analysis and structural investigations

q ¼ 0:162  qs þ 0:838  qs ð2Þ
1 þ kb  p 1 þ ka  p
Differential thermal analysis (DTA) and thermogravimetric
where qs is the saturated adsorption capacity (mol/kg), p is the par- analysis (TGA) have been used to investigate adsorption capacity
tial pressure of the adsorbate (Pa), ka is the equilibrium constant for of 3A and 4A zeolite molecular sieves. Fig. 3a and b shows repre-
cage a (1/Pa), kb is the equilibrium constant for cage b (1/Pa). The sentative DTA (top) and TGA (bottom) curves of molecular sieves
isotherm correlated parameters and the average relative errors for 3A recorded after adsorption of water from the water-ethanol
Langmuir-Langmuir model is shown in Table 2. and water-n-butanol solutions, respectively. On the basis of the
The fitted isotherm constants are obtained by nonlinear DTA-TGA research one can state that the loss of water from the
regression estimation using least squares method according to zeolite molecular sieve samples occurs in the temperature range
Levenberg-Marquard algorithm in program Statistica 10. The 40–400 °C in the case of 3A zeolite molecular sieve and in the range
of 40–500 °C in the case of 4A zeolites. In the DTA curve of 3A
Table 1
molecular sieves recorded after adsorption of water from the
Fitted constants of Langmuir-Freundlich adsorption isotherm. 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.
Parameters and errors Value
On the other hand in the DTA curve for molecular sieves 3A
a0102 (mol/kg) 24.486 recorded after adsorption of water from the water–n-butanol mix-
a1 (1/K) –29.161
a2101 (1/K) 74.336
ture (Fig. 3b, top) one broad endothermic effect is seen up to 500 °C
b0 (1/Pa) –10.659 with three maxima at 130, 230 and 315 °C. In this case simulta-
b1102 (1/K) 19.694 neously recorded TGA curve is also more complex and contains
b2101(1/K) 93.358 one feebly pronounced maximum at 130 °C and inflection at
n0103 (-) –92.940
230 °C (Fig. 3b, bottom). These results are in accord with literature
n1101(1/K) 34.056
d (%) 11.22 data where the endothermic effects in this temperature range are
attributed to desorption of water from the sorbent [31,41,49,50].
236 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242

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

Model Parameters and errors Temperature

100 (°C) 140 (°C) 180 (°C) 200 (°C) 230 (°C) 250 (°C)
Langmuir–Langmuir qs102 (kg/kg) 15.459 15.915 11.757 7.482 4.585 3.875
kb103 (1/Pa) 4.766 5.736 2.292 2.862 0.856 0.834
ka103(1/Pa) 1.512 0.271 0.180 0.209 0.531 0.669
d (%) 4.685 6.725 14.681 14.162 16.315 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

Cycle no. C0 (kg/kg) w104 (m/s) tads (min) tdes (min) mG (kg/m2s) Tr (°C) qd (kg/kg) RL (%)
Ethanol/water/zeolite molecular sieve 3A
E2 0.1424 2.89 125 310 0.306 250 0.169 3.79
E8 0.0738 0.75 512 239 0.306 250 0.160 1.78
E9 0.0508 3.00 320 234 0.306 250 0.163 0.79
E10 0.1412 2.07 276 324 0.238 250 0.166 2.15
E12 0.0894 1.89 277 176 0.272 240 0.162 2.43
E13 0.0993 2.56 153 275 0.306 200 0.129 1.25
n-Propanol/water/zeolite molecular sieve 3A
P2 0.021 2.93 500 290 0.272 250 0.149 1.68
P3 0.032 2.83 340 283 0.306 250 0.164 2.32
P4 0.051 1.75 420 358 0.238 250 0.128 1.52
P5 0.044 4.04 240 360 0.306 250 0.142 2.19
P7 0.034 3.07 330 300 0.272 230 0.124 1.67
n-Butanol/water/zeolite molecular sieve 4A
B1 0.044 4.00 630 380 0.238 250 0.146 1.03
B2 0.040 3.00 600 405 0.204 250 0.149 0.89
B5 0.060 2.00 610 570 0.170 250 0.144 0.86
B7 0.050 2.00 640 320 0.306 250 0.152 0.79
B8 0.035 2.00 710 340 0.272 250 0.148 0.84

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

Fig. 2. Experimental and calculated multitemperature Langmuir-Freundlich iso-
therms 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 temper-
atures (close to 40 °C) a small amounts of alcohols adsorbed by the
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 addi-
tional 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 pat-
terns 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 molec-
ular sieves given in literature [32]. It indicates that heating at tem-
peratures 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, approx-
imately 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. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242 237

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
250–1200 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 absorp-
tion 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
water–alcohol 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 previ-
ous 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

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
The 3A and 4A zeolite molecular sieves both after adsorption 1000 °C and UV–Vis-NIR spectra (graph b) of 3A zeolite after adsorption of water
process and after DTA-TGA measurements have been subjected from ethanol and after DTA-TGA measurement up to 1000 °C.
238 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242
spectra. It indicates that after heat treatment above 800 °C and col-
lapse 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 UV–Vis-NIR investigations. Fig. 5b shows the representative
UV–Vis-NIR spectra of 3A zeolite molecular sieve after adsorption
of water from the water-ethanol mixture (Fig. 5b, bottom) and
after DTA–TGA measurement up to 1000 °C (Fig. 5b, top). The
UV–Vis-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 characteris-
tic 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 adsorp-
tion of water from water-alcohol solutions by 3A and 4A zeolites.
3.5. Fixed bed column studies of zeolites regeneration
The TSA process was applied to the aliphatic alcohols dewater-
ing, where the water adsorption step on the zeolite fixed 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 never-
theless present in macropores and in a film 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 profiles, 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 flowed to con-
denser and next was directed to environment protection column to
avoid emission of the alcohol vapor. The condensate was periodi-
cally 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 roll-
up phenomenon can be explained by the equilibrium effect caused
by temperature changes [28].
The operating conditions of selected runs of the cyclic TSA pro-
cess 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 flux density mG, and desorption temperature Tr. The oper-
ating conditions of cooling step were the same in each cycle: air
mass flux 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 fixed bed relating to total mass of zeolite adsorbent was
defined as the dynamic adsorption qd (kg/kg). The values qd, for
each adsorption-desorption cycle were determined from the com-
plete 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 0.79–3.79% for ethanol; 1.52–2.32% for
n-propanol and 0.79–1.03% for n-butanol, according to combina-
tion 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 flux density. The dynamic adsorp-
tion 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 fixed 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 fulfills this demand. It took
place in the cycles E8, P2, B1, B2, B7, and B8. In other cases the oper-
ation 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 first followed by water. Water
desorption demand energy supply to overcome of bonding forces.
The significance of the heat of adsorption can be seen in the
region of unsteady state profiles at the four fixed-bed heights
and at the outlet. Temperature measurements results at various
heights of the fixed bed are presented in Fig. 7. In this figure 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 inflection 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 specific 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
water
50 ethanol
concentration (g/m )
3
40
30
20
10
0
0 50 100 150 20 0 250 300
time (min)
Fig. 6. Typical concentration breakthrough curves of ethanol and water vapors at
column outlet during TSA desorption step of cyclic process (run E2).
 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242 239

T1 - 0.10 m cycles are presented in Table 3, while Fig. 9 displays the values qd
250 for zeolite molecular sieve 3A used for ethanol dewatering (cycles
T2 - 0.20 m
T3 - 0.40 m 1 through 9, and 17 through 28) and for n-propanol dewatering
200 T4 - 0.60 m (cycles 10 through 16), and for zeolite molecular sieve 4A used
T5 - 0.75 m for n-butanol dewatering.
Temperature ( C)
o

T6 - inlet The experimental results indicate that the value of the average
150
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
100 adsorption value can be attained using adequate process parame-
ters (regeneration temperature and air mass flux density). Influ-
ence of the cycle number on the adsorbent loading is presented
50
in Fig. 9. The increase of adsorption loading in the initial cycles is
observed in comparison with the average values. The values of zeo-
0 lites loadings in the following cycles oscillate around the average
0 50 100 150 200 250 300 350 ones.
Time (min)

Fig. 7. Typical fixed bed temperature breakthrough curves at various column

3.7. Heat of adsorption in two column system
positions during TSA desorption and cooling steps of cyclic process (run E2).
By the choice of the cycle conditions, the heat of adsorption can
be stored in a specific manner that is that heat is retained in the
220 bed before or after breakthrough of the water. The solid zeolite
200 could be integrated at a sufficiently high temperature to the regen-
eration of the bed immediately following the adsorption step. Tem-
180
perature increase in the adsorbent bed at the end of the water
160 adsorption step is due to the heat of adsorption release. It follows
140 that the endothermic water desorption step in the gas phase is
Temperature ( C)

favored when temperature increases. The temperature of the

o

120
adsorbent at the end of the adsorption step may be determined
n-butanol
100 in relation to the feed temperature [53]:
ethanol
80 Dq  DH
n-propanol DT  ð5Þ
60 C AV
40
where DT represents the difference in temperature of the adsorbent
20 between beginning of the adsorption (dewatering stage) and
0 desorption (regeneration stage) steps, DH is the heat of water
0 20 40 60 80 100 120 140 160 180 200 220 240 adsorption, and CAV is the average heat capacity in column (includ-
ing solid adsorbent and liquid loading at the end of the adsorption
Time (min)
step), Dq is the working water adsorptive capacity, defining the dif-
Fig. 8. Temperature profiles during regeneration of zeolite molecular sieves bed ference equilibrium loadings of water (mol/kg) corresponding to
used to dewatering alcohols (runs E12, P2, B8, measured inside bed h = 0.4 m, temperature of the adsorption (dewatering) and the desorption
mG = 0.272 kg/m2s, Tr = 250 °C). (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
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 0.26
reaching of the water boiling point. Furthermore, after attaining
zeolite 3A
the fixed bed temperature of 130 °C, the inflection point appears. 0.24
zeolite 4A
Then, the fixed bed temperature increases to about 200 °C
av 3A (0.1549 kg/kg)
(depending on operating conditions) and remains at the constant 0.22
Adsorption capacity (kg/kg)

av 4A (0.1497 kg/kg)
level. It is probably caused by water release from the b cage. The
course of desorption curve fully corresponds with TGA investiga- 0.2
tion results, revealing the mass loss at the same temperature.
From experimental investigations it results that water adsorp- 0.18
tion capacity of the zeolite fixed beds decreases in subsequent
adsorption cycles to 60–70% in comparison with that obtained on 0.16
fresh adsorbent bed. It is because of incomplete water desorption
0.14
in following regeneration stages in process operating conditions
imposed. The remaining water amount in the bed forms residual
0.12
adsorption.
0.1
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29
3.6. Effect of the number of cycles on adsorption capacity
Cycle number (-)

The dynamic adsorption values qd change depending on opera- Fig. 9. Effect of the number of cycles performed on water adsorption capacity of
tional conditions especially in the TSA process cycles. The selected water on 3A and 4A zeolites fixed bed.
240 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242

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 van’t 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 tem-
perature of 200 °C to 23 °C in temperature of 250 °C. The existing
temperature rises at the moment of fixed bed breakthrough mea-
sured in experiments are higher (increase about 15–35 °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
fixed bed depends on two parameters which describe the specific
hot purge air and energy consumptions. Namely, the purge air
and energy consumptions are functions of regeneration tempera-
ture Tr [28,54]. These parameters are defined 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), respec-
tively. The definitions of the Np and Ep are:
n tdes
Np ¼
qb V b
Ep ¼ Np C pg ðT r  T 0 Þ
C pg ¼ 31:15  1:357  102 ðT r þ 273Þ þ 2:68  105 ðT r þ 273Þ2
 1:168  108 ðT r þ 273Þ3
where n is the molar air flow rate in mol/min, qb is the air bulk den-
sity 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 specific gas consumption Np (kg air/kmol water) values for eth-
anol, n-propanol and n-butanol equal: 0.227; 0.278; 0.294,
respectively.
3
2.8
2.6
Np (kmol / kg adsorbent)
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 min-
imal energy consumption for the investigated systems, appears
in temperature of about 240 °C. In this temperature the specific
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 experimen-
tal 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 pervapora-
tion, 0.84 MJ/kg ethanol and 2.26 MJ/kg water and simultaneously
energy requirement for azeotropic distillation is 3.31 MJ/kg etha-
nol [55]. The above presented data concern of the ethyl alcohol
dewatering in the concentration range of 95–99.5 wt%.
3.9. Determination of the process parameters ensuring efficient zeolite
bed regeneration
The experimental investigations of both the fixed bed column
desorption and loaded zeolite samples thermal analyses were
carried out. They enabled determination of process parameters
ensuring most efficient zeolite bed regeneration in the examined
ð6Þ
variability range. With increase of imposed regeneration tempera-
ture Tr, effectiveness of zeolite bed regeneration increases what
ð7Þ causes also increase of the bed dynamic adsorption capacity in
the subsequent TSA cycle (adsorption step). With increase of the
imposed purge gas mass flux density shortening of desorption step
duration was observed (Table 3).
ð8Þ 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 (230–250 °C),
determined in column investigation, is nearly constant and purge
gas consumption in this temperature range slightly decreases
(Fig. 10). Increasing of air mass flux 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
8
simultaneously safe for adsorbent structure.
7 On the other hand, from the results of experimental measure-
ments it is clear that multiply regeneration of the fixed bed adsor-

2.4
Ep (kJ/ kg adsorbent)

ethanol 6
bent does not influence greatly the adsorbent structural changes.
2.2 n-propanol
5 The dynamic adsorption capacity is maintained on the level about
2 n-butanol
65%.
1.8 4

1.6 3 4. Conclusions
1.4
2
1.2 The investigations have revealed that dewatering of aliphatic
1 alcohols using 3A and 4A zeolite molecular sieves and their regen-
1
eration, in the TSA process, are effective at the operating conditions
0.8 0 determined in this study. The innovative experiments are carried
190 200 210 220 230 240 250 260
o
out in full TSA cycles comprising of dewatering and regeneration
Desorption temeprature ( C)
stages for three water-alcohol systems that are the ethanol,
Fig. 10. Effect of purge air temperature on specific gas consumption Np and effect of n-propanol, and n-butanol. It is evident that the regeneration stage
specific energy consumption Ep. plays a pivotal role in this TSA process. The measurements show
 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242
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 first stage
the intensive alcohol-water solution evaporation takes place (in
temperature about 40 °C), mainly contained in a liquid film of
the zeolite particles surroundings. Next, the loss of water from
the zeolite molecular sieves occurs in the temperature range of
40–400 °C in the case of 3A zeolite molecular sieve and
40–500 °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 destruc-
tion 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 con-
sumptions depend on the operating conditions (i.e. regeneration
temperature, mass air flux 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
specific gas consumption Np and specific 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 pro-
cess should be developed in the near future.
References
[1] D. Antoni, V.V. Zverlov, W.H. Schwarz, Biofuels from microbes, Appl. Microbiol.
Biotechnol. 77 (2007) 23–35.
[2] S. Fernando, S. Adhikari, K. Kota, R. Bandi, Glycerol based automotive fuels
from future biorefineries, Fuel 86 (2007) 2806–2809.
[3] A.B. van der Merwe, H. Cheng, J.F. Görgens, J.H. Knoetze, Comparison of energy
efficiency and economics of process designs for biobutanol production from
sugarcane molasses, Fuel 105 (2013) 451–458.
[4] M. Kumar, Y. Goyal, A. Sarkar, K. Gayen, Comparative economic assessment of
ABE fermentation based on cellulosic and non-cellulosic feedstocks, Appl.
Energy 93 (2012) 193–204.
[5] S. Liu, N. Qureshi, How microbes tolerate ethanol and butanol, New Biotechnol.
26 (2009) 117–121.
[6] J. Swana, Y. Yang, M. Behnam, R. Thompson, An analysis of net energy
production and feedstock availability for biobutanol and bioethanol, Bioresour.
Technol. 102 (2011) 2112–2117.
[7] R. Gheshlaghia, J.M. Scharera, M. Moo-Younga, C.P. Choua, Metabolic pathways
of clostridia for producing butanol, Biotechnol. Adv. 27 (2009) 764–781.
[8] C. Jin, M. Yao, H. Liu, C.F. Lee, J. Ji, Progress in the production and application of
n-butanol as a biofuel, Renew. Sust. Energy Rev. 15 (2011) 4080–4106.
[9] V.I. Agueda, J.A. Delgado, M.A. Uguina, J.L. Sotelo, A. Garcia, Column dynamics
of an adsorption–drying–desorption process for butanol recovery from
aqueous solutions with silicalite pellets, Sep. Purif. Technol. 104 (2013) 307–
321.
[10] M. Kumar, K. Gayen, Developments in biobutanol production: new insights,
Appl. Energy 88 (2011) 1999–2012.
[11] C. Lu, J. Dong, S.T. Yang, Butanol production from wood pulping hydrolysate in
an integrated fermentation-gas stripping process, Bioresour. Technol. 143
(2013) 467–475.
[12] P.A. Mariano, R.M. Filho, Improvements in biobutanol fermentation and their
impacts on distillation energy consumption and wastewater generation,
Bioenerg. Res. 5 (2012) 504–514.
[13] J.F.G. Oliveira, I.L. Lucena, R.M.A. Saboya, M.L. Rodrigues, A.E.B. Torres, F.A.N.
Fernandes Jr., C.L. Cavalcante Jr., E.J. Parente, Biodiesel production from waste
coconut oil by esterification with ethanol: the effect of water removal by
adsorption, Renewable Energy 35 (2010) 2581–2584.
[14] A. Oudshoorn, L.A.M. van der Wielen, A.J.J. Straathof, Adsorption equilibria of
bio-based butanol solutions using zeolite, Biochem. Eng. J. 48 (2009) 99–103.
[15] A. Oudshoorn, L.A.M. van der Wielen, A.J.J. Straathof, Desorption of butanol
from zeolite material, Biochem. Eng. J. 67 (2012) 167–172.
[16] V. Saravanan, D.A. Waijers, M. Ziari, M.A. Noordermeer, Recovery of 1-butanol
from aqueous solutions using zeolite ZSM-5 with a high Si/Al ratio; suitability
of a column process for industrial applications, Biochem. Eng. J. 49 (2010) 33–
39.
[17] P.D. Martin, S.W. Swanton, Improved efficiency of adsorption processes, Appl.
Therm. Eng. 17 (1997) 869–877.
241
[18] J.W. Weaver, S.A. Skaggs, D.L. Spidle, G.C. Stone, Composition and Behavior of
Fuel Ethanol, EPA/600/R-09/037 (2009).
[19] M.J. Carmo, M.G. Adeodato, A.M. Moreira, E.J.S. Parente Jr., R.S. Vieira, Kinetic
and thermodynamic study on the liquid phase adsorption by starchy materials
in the alcohol–water system, Adsorption 10 (2004) 211–218.
[20] S. Al-Asheh, F. Banat, N. Al-Lagtah, Separation of ethanol–water mixtures using
molecular sieves and biobased adsorbents, Chem. Eng. Res. Des. 82 (A7) (2004)
855–864.
[21] T. Yamamoto, Y.H. Kim, B.C. Kim, A. Endo, N. Thongprachan, T. Ohmori,
Adsorption characteristics of zeolites for dehydration of ethanol: evaluation of
diffusivity of water in porous structure, Chem. Eng. J. 181–182 (2012) 443–448.
[22] S. Wang, Y. Peng, Natural zeolites as effective adsorbents in water and
wastewater treatment, Chem. Eng. J. 156 (2010) 11–24.
[23] T.J. Benson, C.E. George, Cellulose based adsorbent materials for the
dehydration of ethanol using thermal swing adsorption, Adsorption 11
(2005) 697–701.
[24] M. Simo, S. Sivashanmugam, Ch.J. Brown, V. Hlavacek, Adsorption/desorption
of water and ethanol on 3A zeolite in near-adiabatic fixed bed, Ind. Eng. Chem.
Res. 48 (2009) 9247–9260.
[25] S.M. Ben-Shebil, Effect of heat of adsorption on the adsorptive drying of solvents
at equilibrium in a packed bed of zeolite, Chem. Eng. J. 74 (1999) 197–204.
[26] A. Lau, B.D. Crittenden, R.W. Field, Enhancement of liquid phase adsorption
column performance by means of oscillatory flow: an experimental study, Sep.
Purif. Technol. 35 (2004) 113–124.
[27] I. Pentchev, K. Paev, I. Seikova, Dynamics of non-isothermal adsorption in
packed bed of biporous zeolites, Chem. Eng. J. 85 (2002) 245–257.
[28] K.S. Hwang, D.K. Choi, S.Y. Gong, S.Y. Cho, Adsorption and thermal
regeneration of methylene chloride vapor on an activated carbon bed, Chem.
Eng. Sci. 52 (1997) 1111–1123.
[29] K. Kupiec, J. Rakoczy, E. Lalik, Modeling of PSA separation process including
friction pressure drop in adsorbent bed, Chem. Eng. Proc. 48 (2009) 1199–
1211.
[30] J.-S. Jeong, H. Jeona, K.-M. Koa, B. Chungb, G.-W. Choi, Production of anhydrous
ethanol using various PSA (Pressure Swing Adsorption) processes in pilot
plant, Renew. Energy 42 (2012) 41–45.
[31] M.M. Abdillahi, M.S. Gharami, A.B. Siddiqui, Characterization of synthesized A-
zeolite. Simultaneous thermal analysis, X-ray diffraction, scanning electron
microscopy and ICP-chemical analysis, J. Therm. Anal. Calorim. 42 (1994)
1275–1284.
[32] D. Breck, W.G. Eversole, R.M. Milton, T.B. Reed, T.L. Thomas, Crystalline zeolite.
I. The properties of a new synthetic zeolite, type A, J. Am. Chem. Soc. 78 (1956)
5963–5971.
[33] K.F. Loughlin, Water isotherm models for 4A (NaA) zeolite, Adsorption 15
(2009) 337–353.
[34] I. Tsibranska, A. Assenov, Experimental verification of the model of adsorption
in biporous particles, Chem. Eng. Proc. 39 (2000) 149–159.
[35] A. Gupta, V. Gaur, N. Verma, Breakthrough analysis for adsorption of sulfur-
dioxide over zeolites, Chem. Eng. Proc. 43 (2004) 9–22.
[36] D. Ko, M. Kima, I. Moona, D. Choi, Analysis of purge gas temperature in cyclic
TSA process, Chem. Eng. Sci. 57 (2002) 179–195.
[37] A. Casas, M.J. Ramos, A. Perez, Adsorption equilibrium and kinetics of methyl
acetate/methanol and methyl acetate/water mixtures on zeolite 5A, Chem.
Eng. J. 220 (2013) 337–342.
[38] J.L. Sotelo, M.A. Uguina, J.A. Delgado, L.I. Celemin, Adsorption of methyl ethyl
ketone and trichloroethene from aqueous solutions onto activated carbon
fixed-bed adsorbers, Sep. Purif. Technol. 37 (2004) 149–160.
[39] A. Martucci, L. Pasti, N. Marchetti, A. Cavazzini, F. Dondi, A. Alberti, Adsorption
of pharmaceuticals from aqueous solutions on synthetic zeolites, Micropor.
Mesopor. Mater. 148 (2012) 174–183.
[40] E. Lalik, R. Mirek, J. Rakoczy, A. Groszek, Microcalorimetric study of sorption of
water and ethanolin zeolites 3A and 5A, Catal. Today 114 (2006) 242–247.
[41] M. Afzal, G. Yasmeen, M. Saleem, P.K. Butt, A.K. Khattak, J. Afzal, TG and DTA
study of the thermal dehydration of metal-exchanged zeolite-4A samples, J.
Therm. Anal. Calorim. 62 (2000) 721–727.
[42] B. Ambrozek, _ J. Nastaj, E. Gabruś, Modeling and experimental studies of
adsorptive dewatering of selected aliphatic alcohols in temperature swing
adsorption system, Dry. Technol. 31 (2013) 1780–1789.
[43] J. Nastaj, T. Aleksandrzak, Adsorption isotherms of water, propan-2-ol, and
methylbenzene vapors on grade 03 silica gel, Sorbonorit 4 activated carbon,
and HiSiv 3000 zeolite, J. Chem. Eng. Data 58 (2013) 2629–2641.
_
[44] B. Ambrozek, J. Nastaj, E. Gabruś, Modeling of adsorptive drying of n-propanol,
Dry. Technol. 30 (2012) 1072–1080.
[45] S. Brunauer, L.S. Deming, W.E. Deming, E. Teller, On a theory of the van der
Waals adsorption of gases, J. Am. Chem. Soc. 62 (1940) 1723–1732.
[46] E. Alver, A.U. Metin, Anionic dye removal from aqueous solutions using
modified zeolite: adsorption kinetics and isotherm studies, Chem. Eng. J. 200–
202 (2012) 59–67.
[47] O.A. Hougen, K.M. Watson, Chemical Process Principles, New York 1947.
[48] F. Tümsek, O. Inel, Evaluation of the thermodynamic parameters for
adsorption of some n-alkanes on A type zeolite crystals by inverse gas
chromatography, Chem. Eng. J. 94 (2013) 57–66.
[49] P.C. Borthakur, B.D. Chattaraj, Study of Na-A molecular sieve degeneration by
thermal analysis, J. Therm. Anal. Calorim. 17 (1979) 67–72.
[50] A. Radulovic, V. Dondur, R. Dimitrijevic, D. Arandjelovic, Thermal
transformation of Na-LTA into low-carnegieite: the influence of residual
sodium and aluminium species, Thermochim. Acta 511 (2010) 37–42.
242 E. Gabruś et al. / Chemical Engineering Journal 259 (2015) 232–242

[51] S.P. Kamble, P.A. Mangrulkar, A.K. Bansiwal, S.S. Rayalu, Adsorption of phenol
and o-chlorophenol on surface altered fly ash based molecular sieves, Chem.
Eng. J. 138 (2008) 73–83.
[52] G. Moussavi, S. Talebi, M. Farrokhi, R.M. Sabouti, The investigation of
mechanism, kinetic and isotherm of ammonia and humic acid co-adsorption
onto natural zeolite, Chem. Eng. J. 171 (2011) 1159–1169.
[53] M.W. Ackley, S.U. Rege, H. Saxena, Application of natural zeolites in the
purification and separation of gases, Micropor. Mesopor. Mater. 61 (2003) 25–42.
[54] J.-H. Yun, D.-K. Choi, H. Moon, Benzene adsorption and hot purge regeneration
in activated carbon beds, Chem. Eng. Sci. 55 (2000) 5857–5872.
[55] E. Nagy, S. Boldyryev, Energy demand of biofuel production applying
distillation and/or pervaporation, Chem. Eng. Trans. 35 (2013) 265–270.