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# 2004 Institution of Chemical Engineers
www.ingentaselect.com=titles=02638762.htm Trans IChemE, Part A, May 2004
Chemical Engineering Research and Design, 82(A5): 667–681

ADSORPTION OF XYLENES ON FAUJASITE-TYPE ZEOLITE

Equilibrium and Kinetics in Batch Adsorber
M. MINCEVA and A. E. RODRIGUES*
Laboratory of Separation and Reaction Engineering, University of Porto, Porto, Portugal

T
he adsorption of p-xylene, o-xylene and ethylbenzene on ion-exchanged fuajasite type
zeolite has been studied in liquid phase at 30, 50, 80, 120 and 180
C. The single
adsorption isotherms have been measured in a batch mode. The Langmuir and Sips
isotherm have been used to describe the experimental adsorption isotherm data. The Sips
equation fits the experimental isotherm data better than the Langmuir model. The saturation
adsorption capacity of the adsorbent was similar for all components (around 1 mol kg1). The
p-xylene is the more strongly adsorbed component followed by ethylbenzene and o-xylene.
The heat of the adsorption was 27.2 kJ=mol1 for p-xylene, 20.3 kJ=mol1 for ethylbenzene
and 18.5 kJ=mol1 for o-xylene. The kinetics of adsorption of p-xylene, o-xylene and
ethylbenzene was also studied. The xylene uptake curves have been described by a mathematical
model that accounts for the macropore and=or micropore diffusion as rate controlling mechanisms.
It was found that, for temperatures lower than 80
C in the case of p-xylene and lower than 50
C for
o-xylene and ethylbenzene, both macropore and micropore diffusion contribute to the rate of
adsorption. At higher temperatures macropore diffusion is the rate-controlling mechanism.

Keywords: xylenes; faujasite zeolite; adsorption; equlibrium; kinetics; modelling.

INTRODUCTION 1970), Toray’s Aromax (Otani et al., 1973) and IFP’Eluxyl

Mixed xylenes refer to a mixture of C8 aromatic isomers that
includes p-xylene, m-xylene, o-xylene and ethylbenzene.
The feedstocks and processes used to manufacture xylenes
include petroleum reformate (80–95.4%), pyrolysis gasoline
(4–11.1%), toluene disproportionation (0.4–7.6%), and
coke oven light oil (0.2–1.3%; Fabri and Veba, 2002). The
applications of xylenes are presented in Table 1. More than
half of mixed xylenes produced is used in form of pure
xylene. The most important xylene isomer is p-xylene, which
is produced in the highest quantity (45.5%). The p-xylene is
used exclusively for making dimethyl terephthalate and
terephthalic acid (DMT=TPA), which are raw materials used
in the manufacture of polyethylene terephthalate (PET) for
polyester fibers, molded plastics, films and blown beverage
bottles. With the exception of xylene production by dispro-
portination of toluene, the xylene isomers and ethylbenzene
are always produced as a mixture in all production processes.
These isomers have similar boiling points and therefore their
separation by conventional distillation is not practical.
The industrial separation of p-xylene is generally performed
by simulated moving bed (SMB) technology. There are three
main industrial processes: UOP’s Parex (Broughton et al.,
*Correspondence to: Professor A.E. Rodrigues, Laboratory of Separation
and Reaction Engineering (LSRE), Department of Chemical Engineering,
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s=n,
4200-465 Porto, Portugal.
E-mail: arodrig@fe.up.pt
(Ash et al., 1994). The SMB is a continuous chromatographic
counter-current process developed in 1960s by Universal Oil
Products (Broughton and Gerhold, 1961). The SMB unit
consists of a set of columns connected in series; the counter-
current flow of solid and liquid phases is simulated by the
periodic shifting of inlet and outlet streams in the direction of
the fluid flow. Separation is accomplished by exploiting the
differences in affinity of the adsorbent for p-xylene relative to
the other C8-isomers on faujasite-type zeolites, among which
prehydrated KY and BaX zeolite hold an important place. The
industrial SMB units operate in liquid phase at temperature
around 180
C and pressure around 9 bar.
Despite the commercial importance of the xylene
isomers, available information concerning the equilibrium
isotherms and heats of sorption is fragmentary and often
contradictory. The C8 aromatics are strongly adsorbed on
zeolites of the X and Y types and the isotherms are of the
highly favourable type I form (Ruthven and Goddard, 1986).
The equilibrium of adsorption of single xylene in liquid
phase has been studied on different types of ion exchanged
faujasite type of zeolites: KY (Santacesaria et al., 1982a;
Neves, 1995), BaX (Moya-Korchi, 1995) and K-BaY (Hsiao
et al., 1989). In all studies the equilibrium of adsorption
has been measured at low temperature (20–80
C); and
Langmuir or Sips isotherm have used to describe the
equilibrium data. All faujasite ion exchanged zeolites have
shown similar adsorption capacity (1–1.75 mol kg1).
Tournier et al. (2001) have studied the single m-, p-xylene
and p-diethylbenzene adsorption isotherm on a prehydrated

667
668 MINCEVA and RODRIGUES
Table 1. Application of xylenes.
EXPERIMENTAL SECTION
Feedstock Application wt% Materials
Mixed xylenes Solvent use 5.2
Mixed xylenes Aviation fuel and gasoline 39.3
Adsorbent
p-Xylene Dimethyl terephthalate (DMT) 45.8 The reference adsorbent is ion-exchanged faujasite-type
and terephthalic acid (TPA) of zeolite. The adsorbent is in form of spherical pellets with
o-Xylene Phthalic anhydride 7.7 a diameter between 0.3 and 1 mm. The average pellet
m-Xylene Isophthalic acid 2.0 diameter calculated from the particle size distribution analy-
sis was 0.62 mm. The adsorbent was characterized by SEM

BaX zeolite in vapour phase and binary and ternary xylene

mixtures in liquid phase at 130 and 175
C. The adsorption
equilibrium of single components has shown that there are no
important difference between m-, p-xylene and p-diethylben-
zene. In the case of xylene mixture, the selectivities depend
strongly on the composition of the liquid phase and the
temperature. The presence of the third component changes
the binary selectivity. Similar results were obtained by
Paludetto et al. (1987) in the study of the adsorption equilibria
of two ternary systems involving m-xylene, p-xylene, and
either toluene or isopropylbenzene in vapour phase at 150 and
170
C on zeolite K-Y. The highly non-ideal behaviour has
been found for the mixtures of apparently quite similar
components, such as m- and p-xylene and toluene, which lead
to selectivity values strongly dependent upon composition.
The potential of using medium-pore-size zeolites, instead
of large-pore zeolites, for xylene separation has been inves-
tigated by Yan (1989). He found that ZMS-5 with a high
SiO2:Al2O3 ratio is highly selective for p-xylene adsorption,
and the selectivity for p-xylene over ethylbenzene can be as
high as 5.5.
Ruthven and Goddard (1986) carried out a detailed
experimental study of the equilibrium behaviour of the
four C8 aromatics isomers (o-, m-, p-xylene and ethylben-
zene) in the vapour phase, on Na-X, Na-Y and K-Y zeolite
crystals at temperatures in the range 130–200
C. At low
loading a small difference in the Henry’s constants for the
four isomers on K-Y, Na-Y and Na-X has been found. The
separation factors increase with loading and in some cases
the affinity sequence at high loadings is reversed.
Santacesaria et al. (1982a, b) studied the xylene isomers
adsorption in liquid phase on potassium-exchanged Y
zeolite. The experimental runs performed on KY crystals
and pellets have confirmed that the diffusion rate in the
microcrystals is very high and diffusion in the macropore is
the rate-controlling mechanism.
Moya-Korchi (1995) investigated the kinetics of adsorp-
tion of p- and o-xylene on KBa-Y and found that micropore
diffusion is the rate-controlling mechanism from 9 to 20
C;
at 20
C both micropore and macropore diffusion contribute
to the rate of the adsorption; above 30
C the macropore
diffusion becomes the rate-controlling mechanism.
Sorption kinetics of toluene, p-xylene, o-xylene, toluene
and p-diethylbenzene onto Y zeolite pellets at temperatures
between 150 and 210
C have been studied by Cavalcante
et al. (1997). According to the authors neither macropore
or micropore diffusion control models are able to fully
represent the experimental data.
The aim of this work is to study the equilibrium and
kinetics of adsorption of xylenes on Ba exchanged
faujasite-type of zeolite in liquid phase in a wide tempera-
ture range, including the temperature (180
C) and pressure Figure 1. SEM photographs of the adsorbent, magnified (a) 4000 and (b)
(9 bar) used in industrial separation by SMB technology. 10,000.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
 ADSORPTION OF XYLENES
Table 2. Mercury porosimetry and helium picnometry analysis.
Mercury porosimetry analysis
Total volume of intrusion (  20,000–30,000 psia) 0.218 ml g1
Total area of pores 7.58 m2 g1
Average pore diameter (based on volume: 4. V=A) 1150 Å
Apparent density 1.48 g ml1
Solid density (30,000 psia) 2.19 g ml1
Porosity 0.32
Helium picnometry analysis
Solid density 2.35 g ml1
Porosity 0.37
analysis, X ray microanalysis (performed by CEMUP-
Centro de Materiais da Universidade do Porto), helium
picnometry and mercury porosimetry (performed by I.P.N.
Labgran, Laboratório de caracterização e certificação de
materias granulares). The SEM analysis (Figure 1) showed
that the crystal size is 1–2 mm. The X-ray microanalysis has
revealed Ba as exchanged ion. The results of helium picno-
metry and mercury porosimetry analysis are summarized in
Table 2.
The selectivity of ion exchanged faujasite-type zeolites to
p-xylene depends on the pre-adsorbed water in the zeolite.
According to the literature data, X and Y ion-exchanged
zeolites show a maximum selectivity to p-xylene when the
adsorbent water content is between 2 and 6 wt% (Zinnen,
1992; Furlan et al., 1992; Neves, 1995; Tournier et al.,
2001). It was shown that the water content of the adsorbent
could be controlled by the temperature of drying applied in
the thermal treatment of the adsorbent (Furlan et al., 1992;
Neves, 1995). The dependence of the adsorbent water
content on the temperature of drying was determined by
the following procedure: (i) the adsorbent was exposed on
air for 48 h and placed in glass column; (ii) the column was
placed in a cylindrical oven (Termolab, Portugal); (iii) the
column was connected to a helium bottle and He flow
adjusted (0.5 dm3 min1) with a mass flowmeter (Model
400, Hastings instruments); (iv) the adsorbent was heated
to 120
C (2
C min1), and held at 120
C for 24 h; at the end
of the experiment the adsorbent was cooled down to ambient
Figure 2. Weight percentage of the water in the adsorbent as a function of
temperature of drying: (D) KBaX (Furlan et al., 1992); (u) KY (Neves,
1995); (e) Ba-exchanged faujasite zeolite (this work).
Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
669
temperature under flow of He; and (v) the quantity of the
water desorbed at 120
C was calculated as a difference
between the mass of the column and adsorbent before and
after the thermal treatment.
The procedure [steps (i)–(v)] was repeated at 200, 250,
300, 350 and 400
C using the same adsorbent. The weight
percentage of water in the adsorbent as a function of
temperature of drying is presented in Figure 2. In the
same figure the relations obtained by Neves (1995) for
zeolite KY and Furlan et al. (1992) for zeolite KBaX are
presented. All adsorbents show similar dependence of the
water content from the temperature of drying. The tempera-
ture of 250
C (3 wt% H2Oin the adsorbent ) was chosen for the
treatment of the Ba-exchanged faujasite zeolite used in the
adsorption equilibrium and kinetics experiments.
Reagents
The p-xylene, o-xylene and ethylbenzene of GC grade
(purity >99%; Fluka, Switzerland) were used as adsorbates.
According to the literature data, m-xylene has very similar
adsorption equilibrium on faujasite type zeolites to o-xylene
(Neves, 1995; Santacesaria et al., 1982a, b); therefore, it was
not considered in the adsorption study. i-Octane of 98%
purity (Fluka, Switzerland) was used as a solvent. The
i-octane has the same kinetic diameter as p-xylene (6.7 Å)
and is not adsorbable on X and Y type zeolites (Moya-
Korchi, 1995).
Experimental Set-up
The experiments were carried out in a glass jacketed 1 dm3
autoclave (Büchi, Switzerland), operating in a batch mode.
The adsorber was equipped with mechanically stirrer,
pressure and temperature sensors (Figure 3). Temperature
was controlled by silicone oil thermostatic bath (Ecoline306
Lauda, Germany). To maintain the xylene=i-octane mixture in
liquid phase over the whole temperature range, the adsorber
was pressurized by helium to 9 bar. The adsorbent (30 g) was
placed in a basket at the top of the stirrer shaft, and fell down
in the xylene=i-octane solution at the beginning of the
Figure 3. Experimental set-up. 1, Batch adsorber; 2, basket for the
adsorbent (up and down position); 3, temperature sensor; 4, motor; 5,
pressure sensor; 6, helium bottle; 7, thermostatic bath; 8, sampling valve; 9,
gas chromatography; 10, acquisition board and computer.
670 MINCEVA and RODRIGUES

agitation (time zero; Silva and Rodrigues, 2001). The

sampling was automatic; one of the outlets of the adsorber
was connected to the 0.1 ml liquid sampling valves (Valco,
USA). The samples were analysed with a gas chromatograph
(Chrompack 9100, Netherlands) equipped with wide bore
injector, fused silica capillary column (WCOT-CP
XYLENES-Chrompack, 0.21 mm diameter, 10 m length)
and flame ionization detector (FID). The column temperature
was 30
C, the injector and detector temperatures were 150
C.
Helium (28 ml min1) was used as carrier gas.

Experimental Procedure
A volume of 0.35–0.4 dm3 of single xylene solution in i-
octane with an initial concentration of between 1 and
10 wt% was introduced in the adsorber. For each experiment
(adsorption equilibrium or kinetics), around 30 g of the pre-
treated adsorbent (3 wt% H2O in the adsorbent) was trans-
ferred from the glass column used in the thermal treatment
to the basket under the flow of He. After that the basket was
placed at the top of the stirrer shaft in the adsorber; the
adsorber was closed and pressurized with He. When the
operation conditions were reached the mixing was started;
the basket fell down along the stirrer shaft and contacted
the xylene=i-octane solution (time zero in the kinetics
experimets).

EQUILIBRIUM OF ADSORPTION
The equilibrium of adsorption of p-xylene, o-xylene and
ethylbenzene on Ba-exchanged faujasite was measured at
30, 50, 80, 120 and 180
C. The equilibrium experiments
were performed in the batch mode using the experimental
set-up and procedure described above. The equilibrium was
reached in 20 min at the highest temperature (180
C) and a
few hours at the lowest temperature (30
C, in the case of
p-xylene).
The experimental adsorption equilibrium data of
p-xylene, o-xylene and ethylbenzene at 30, 50, 80, 120
and 180
C are presented in Figure 4(a–c) respectively.
The adsorption equilibrium data were described by the
Langmuir and Sips isotherm. The Langmuir isotherm is:
qm bc
q ¼ (1)
1 þ bc


Q
b ¼ b1 exp (2)
RT
where q* is the equilibrium adsorbed concentration, qm is
the saturation capacity, b is the affinity or Langmuir
constant, b 1 pre-exponential factor in constant b, Q is Figure 4. Experimental isotherm at different temperatures: (a) p-xylene; (b)
o-xylene and (c) ethylbenzene.
the isosteric heat of the adsorption, R is the gas constant, T is
the temperature and c* is the equilibrium liquid phase
concentration.
The Sips equation (Sips, 1948) is: Qy ¼ 0.5 is the isosteric heat at the fractional loading of 0.5
 1=n (Do, 1998).
qms (bs c )
q ¼ (3) The Langmuir isotherm parameters have been calculated
[1 þ (bs c )1=n ] from the experimental data by linearization of the Langmuir


Qy¼0:5 equation:
bs ¼ bs1 exp (4)
RT
where qms, bs and n are the Sips equation parameters, bs1 is 1 1 1 1
¼ þ (5)
the adsorption affinity constant at infinite temperature, and q qm b c  qm

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
 ADSORPTION OF XYLENES 671

This correlation gives more weight to very low concentra-
tions. According to the literature data (Moya-Korchi, 1995;
Neves, 1995) and experimental adsorption isotherms obtained
in this work, the xylene isotherms are very steep and have
similar saturation capacities. Therefore, a good description of
the experimental data in the linear region is important for
the correct determination of the xylene selectivities.
The Sips equation parameters were estimated from the
experimental equilibrium data using non-linear regression
software REPROCHE (Regression Program for Chemical
Engineers, Version 7, ChemEng Software, 1992). Initially
all three parameters were calculated. Than, the average value
of the maximum capacity (qms) for all temperatures was
fixed and the fitting of the experimental isotherm data was
repeated to find the other two parameters (bs and n) of the
Sips equations.
The Langmuir and Sips parameters for p-xylene, o-xylene
and ethylbenzene, together with the average relative devia-
tion, are presented in Table 3. The average relative deviation
was calculated using the following equation:
1X N
jqexp  qcal j
ARD% ¼  100 (6)
N i¼1 qexp
where N is the number of the experiments qexp is the
adsorbed concentration measured experimentally and qcal
is the adsorbed concentration calculated by the isotherm
equation (Langmuir or Sips).
The Ba-exchanged faujasite used in this work has similar
saturation capacities for all three components. The satura-
tion capacity for p-xylene is slightly higher than that for
ethylbenzene and the saturation capacity for ethylbenzene is
sligthly higher than that of o-xylene. In Table 4 the satura-
tion capacities of different types of ion-exchanged zeoilites
found in the literature are presented. The adsorbent used in

Table 3. Langmuir and Sips isotherm parameters.

Langmuir isotherm Sips isotherm

T,
C b, dm3 mol1 qm, mol kg1 ARD, % bs, dm3 mol1 qms, mol kg1 n ARD, %
p-Xylene
30 41519.0 1.105 4.85 47110.0 1.300 5.828 4.86
50 3606.5 1.103 8.15 3242.0 1.300 4.499 5.58
80 1411.8 0.979 6.62 988.6 1.300 4.163 3.61
120 786.4 0.971 9.49 359.4 1.300 3.632 5.72
180 206.9 0.961 12.16 92.8 1.300 2.821 2.82
o-Xylene
30 1029.9 0.925 10.20 232.4 1.200 2.799 5.28
50 408.6 0.917 11.11 116.4 1.200 2.457 4.76
80 295.2 0.890 13.48 71.6 1.200 2.342 6.12
120 157.1 0.891 14.81 46.3 1.200 2.269 4.52
180 94.7 0.860 13.93 28.5 1.200 2.07 2.07
Ethylbenzene
30 1464.9 0.997 8.56 647.1 1.250 3.137 4.60
50 500.9 0.990 7.10 254.2 1.250 2.756 1.00
80 321.1 0.973 6.32 159.0 1.250 2.692 1.23
120 139.0 0.980 4.93 69.9 1.250 2.235 1.96
180 109.4 0.906 3.72 38.5 1.250 2.376 3.76

Table 4. The saturation adsorption capacity and heat of adsorption of xylenes on different types of ion exchanged faujasite zeolites in a liquid phase.

Adsorbent=solvent=T (
C) Sorbate qm, mol kg1 DH, kJ mol1 Reference

Ba exchanged faujasite=i-octane=30–180
C p-Xylene 1.11–0.96 27.2(Qy ¼ 0.5 ¼ 32.8) This work
o-Xylene 0.93–0.86 18.6(Qy ¼ 0.5 ¼ 15.3)
Ethylbenzene 1.00–0.91 20.3(Qy ¼ 0.5 ¼ 20.8)
KBa-Y=n-heptane=25
C p-Xylene 1.32 — Hsiao et al. (1989)
m-Xylene 0.84
Ethylbenzene 1.13
p-Diethylbenzene 0.83
KBa-Y=i-octane=9–50
C p-Xylene 1.28–1.37 25.6 Moya-Korchi (1995)
o-Xylene 1.29 —
K-Y=n-octane=20–57
C p-Xylene 1.75 8.9 Santacesaria et al. (1982a, b)
o-Xylene 1.75 7.8
m-Xylene 1.75 7.8
Ethylbenzene 1.75 8.0
K-Y=n-octane=20–80
C p-Xylene 1.23 26.6 Neves (1995)
o-Xylene 1.23 26.8
m-Xylene 1.23 24.3
Ethylbenzene 1.23 29.2

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672 MINCEVA and RODRIGUES

this work has a saturation capacity similar to the adsorbents vary with the loading. It can be determined at a given
used by the other researchers. loading by the van’t Hoff equation:
The Sips equation gives better presentation than the
Langmuir equation of the experimental data for all compo-
nents in all temperature ranges (Figure 5).
The isosteric heat of adsorption was calculated from the

Langmuir and Sips equation using the parameters given in DH @ ln c
¼  (7)
Table 4. The isosteric heat of adsorption may or may not RT 2 @T q

Figure 5. Adsorption equilibrium data at: (a) 30
C; (b) 50
C; (c) 80
C; (d) 120
C; and (e) 180
C; fitted with the (——) Langmuir and (- - - -) Sips isotherm.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
 ADSORPTION OF XYLENES
Figure 6. Isosteric heat of adsorption as a function of adsorbent loading:
(s) p-xylene; (j) ethylbenzene; (D) o-xylene.
In this study the isosteric heat of adsorption at given
loading was approximately calculated using an integrated
Clapeyron relationship (Snyder, 1969):
ln (c2 =c1 )
DH  R (8)
((1=T1 )  (1=T2 ))
The isosteric heat of adsorption of p-xylene, o-xylene
and ethylbenzene as function of the adsorbent loading is
presented in Figure 6. The isosteric heat of adsorption
decreases slightly with the loading. The calculated average
values of isosteric heat of adsorption are given in Table 4.
In the case of the Sips equation the isosteric heat at the
fractional loading of 0.5 was calculated by linearization of
equation (4):
Qy¼0:5
ln bs ¼ ln bs1 þ
RT
Figure 7. lnbs vs 1=T for: (s) p-xylene; (j) ethylbenzene; (D) o-xylene.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
673
The lines ln bs vs 1=T are presented in Figure 7. The
calculated values of isosteric heat at the fractional loading
of 0.5 are given in Table 4.
The isosteric heat of adsorption calculated from Langmuir
and Sips equations are slightly different. The p-xylene has
higher isosteric heat of adsorption followed by ethylbenzene
and o-xylene. The isosteric heat of adsorption of p-xylene,
o-xylene and ethylbenzene on Ba-exchanged faujasite
zeolite used in this study has similar values to those found
in the literature, except the values calculated by Santacesaria
et al. (1982a, b).
KINETIC OF ADSORPTION
The kinetics of adsorption were measured at 30, 50, 80,
120 and 180
C as was described previously (around 30 g
of the adsorbent with pre-established water percentage
content 3–4 wt%; 0.35–0.45 dm3 xylene=i-octane solution
with initial concentration 1–10 wt%). The summary of the
kinetics experiments performed is presented in Table 5.
Modelling and Simulation of Adsorption Kinetics
Adsorption calculations and model formulation require the
prediction of adsorbate uptake rate by adsorbent particles.
The zeolite pellets are formed by binding a large number of
microporous crystals (Figure 8). Most of the adsorption
capacity is accommodated in these crystals. The void between
the crystals forms a network of large pores (0.1–1 mm), called
macropores. The macropores act as passage for the molecules
to diffuse from the surrounding fluid into the interior of
the pellet. The mass transfer into the macropores normally
occurs by molecular diffusion. Once the molecules are
adsorbed at the pore mouth of the microparticles, they will
diffuse in the interior of the micropore crystals. The pore size
of the crystals is of the order of the molecular dimension,
therefore diffusing molecules are always within the force field
on the adsorbing surface and their transport takes place in the
form of ‘molecule hopping’ between adsorption sites. Thus
the process is similar to surface diffusion, except that the
domain through which diffusing molecules migrate is not a
two-dimensional surface but rather a three-dimensional space
(Do, 1998).
(9)
Since there are two diffusion mechanisms in the particle, it
is possible that one of them or both control the uptake,
depending on the system parameters and operating condi-
tions. According to the literature, the diffusion in the macro-
pore is the rate-controlling mechanism for the adsorption of
the xylenes in faujasite type of zeolites (Santacesaria et al.,
1982a, b; Neves, 1995). Therefore the mathematical model
considering macropore diffusion and instantaneous adsorp-
tion in the micropore crystals was considered in the description
of the kinetics of adsorption of p-xylene, o-xylene and
ethylbezene onto Ba-exchanged faujasite adsorbent.
Macropore Diffusion Model
The macropore diffusion model considers the diffusion
in the macropore as the rate-controlling mechanism. The
mathematical model is based on following assumptions:
(1) the adsorbent particle has a bidisperse structure contain-
ing macropores and micropores;
674 MINCEVA and RODRIGUES
Table 5. Experiments conditions and model parameters.

Experiment no.

T ( C) m (g) Vl (dm3) co (mol dm3) Dp (cm2 s1) Dc0 (cm2 s1)
p-Xylene
1 30 30.2 0.35 0.054 1.40  106 8.00  1015
2 50 30.2 0.36 0.050 1.92  106 2.50  1014
3 80 28.7 0.38 0.049 2.99  106 —
4 80 30.8 0.38 0.160 2.99  106 —
5 120 31.6 0.40 0.047 4.64  106 —
6 120 28.9 0.35 0.318 4.64  106 —
7 180 28.8 0.45 0.041 8.62  106 —
8 180 31.5 0.45 0.093 8.62  106 —
9 180 29.4 0.45 0.105 8.62  106 —
o-Xylene
10 30 29.6 0.41 0.163 1.42  106 1.5  1014
11 50 32.7 0.42 0.039 1.95  106
12 80 29.3 0.43 0.098 3.03  106 —
13 80 30.3 0.43 0.278 3.03  106 —
14 120 30.1 0.45 0.408 4.70  106 —
15 120 30.8 0.45 0.372 4.70  106 —
16 180 28.9 0.51 0.060 8.72  106 —
Ethylbenzene
17 30 31.4 0.40 0.154 1.41  106 4.5  1014
18 50 29.7 0.42 0.044 1.94  106 —
19 80 28.8 0.45 0.275 3.02  106 —
20 120 31.0 0.46 0.429 4.67  106 —
21 180 31.0 0.51 0.060 8.67  106 —

Initial and boundary conditions

cp (R, 0) ¼ 0 0  R  Rp (11)
@cp
(0, t) ¼ 0 t>0 (12)
@R
cp (Rp , t) ¼ c(t) t>0 (13)

where R is the radial distance from the center of the pellet; t

is the time; cp is fluid phase concentration in the macro-
Figure 8. Idealized presentation of commercial zeolite pellet.
pores; c is bulk fluid phase concentration; q is adsorbed
phase concentration; rp is the adsorbent particle density; Rp
(2) the particles and the crystals have spherical geometry, is the radius of the pellet, ep is particle porosity; and Dp is
the effective pore diffusivity. The effective pore diffusivity is
and are with homogeneous size;
assumed independent of concentration and is estimated
(3) the external mass transfer is neglected due to efficient using the following equation:
mixing of the xylene=i-octane solution (see Appendix);
(4) the internal diffusion in the macropores of the adsorbent ep D m
particle is rate-controlling, instantaneous equilibrium Dp ¼ (14)
t
between the liquid phase in the macropore and the
crystals; where Dm is molecular diffusivity (cm2 s1) and t is
(5) the adsorption equilibrium is of Langmuir type; adsorbent particle tortuosity. The molecular diffusion of p-
(6) constant temperature (temperature was kept constant xylene, o-xylene and ethylbenzene in i-octane were esti-
along each experiment by circulation of silicone oil mated using the Wilke–Chang method:
from the thermal bath through the reactor jacket and
efficient mixing of xylene=i-octane solution). 7:4  108 (fMB )1=2 T
DoAB ¼ (15)
ZB VA0:6

Model Equations The molar volume of p-xylene, o-xylene and ethylbenzene

in the temperature range between 30 and 180
C was calcu-
Mass balance in the volume element of the pellet lated using the Gunn–Yamada method (Reid et al., 1998).
  The viscosity of i-octane at low temperature was calculated
@cp @q 1 @ @cp using the Hildebrand-modified Batschinski equation (Reid
ep þ rp ¼ 2 Dp R2 et al., 1998) and at high temperature [reduced temperature
@t @t Rp @R @R
above 0.7, Tr( ¼ T=Tc) > 0.7] using the Letsou and Stiel
0  R  Rp t>0 (10) relation (Reid et al., 1998) for saturated liquids.

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 ADSORPTION OF XYLENES 675

Langmuir isotherm
qm bcp
q¼ (16)
1 þ bcp

Overall adsorber mass balance

 
dc 1e 3 @cp 
¼ D  (17)
dt e Rp p @R R¼Rp

where e was the external (batch) porosity.

Vl
e¼ (18)
Vl þ Vp
Vl and Vp are the liquid phase and pellet volume,
respectively.

Initial condition
c(0) ¼ c0 (19)
where c0 is bulk fluid phase initial concentration (mol dm3).

Numerical solution of the model equations

Model equations [equations (10)–(19)] were solved using
gPROMS (General Process Modelling System, version 1.7,
Process Systems Enterprise Ltd, 1999). The Orthogonal
collocation method of finite elements (OCFEM) was used
for the discretization of the radial domains. Twenty equal
elements per particle with two internal collocation points
were used in the OCFEM method. For a typical simulation,
a CPU time of about 5 s is required with a Pentium III
726 MHz processor.

Simulation results
The model parameters used in the simulation of each
uptake experiment are given in Table 5, the isotherm
parameters are presented in Table 3 and adsorbent properties
in Table 2.
The mathematical model [equations (10)–(19)] describes
well the p-xylene uptake curves in a temperature range
between 80 and 180
C (Figure 9); and o-xylene and
ethylbenzene uptake curves at temperatures between 50
and 180
C (Figures 10 and 11, respectively). For all the
experiments the tortuosity factor (t) which fits the experi-
Figure 9. p-Xylene uptake curves (experimental and simulated with
mental kinetics data is 7. macropore diffusion model) at (a) 80
C (j, experiment 4; D, experiment
The mathematical model does not fit the experimental 3); (b) 120
C (j, experiment 6; D, experiment 5); (c) 180
C (j, experi-
p-xylene uptake curves at 30 and 50
C, and o-xylene and ment 9; D, experiment 8; r, experiment 7).
ethylbenzene uptake curves at 30
C. This is an indication
that macropore diffusion is not the only rate-controlling
mechanism; some additional mass transfer mechanism diffusion contribute to the determination of the rate of
contributes to the rate of adsorption. The external mass the adsorption, and above 30
C the macropore diffusion
transfer is eliminated by the efficient mixing; therefore, the becomes the rate-controlling mechanism. The reference
additional controlling mass transfer is micropore (crystal) faujasite-type adsorbent used in this study showed similar
diffusion. behaviour, the only difference being that the eventual shift
The change of the mass transfer control from macropore of the macropore to micropore diffusion as control mechan-
diffusion to micropore (crystal) diffusion with decrease ism happens at a higher temperature (between 50 and 80
C
of the temperature was also observed by Moya-Korchi, for p-xylene and between 30 and 50
C for o-xylene and
(1995). In this work KBa-Y zeolite and i-octane are used ethylbenzene). This should be confirmed by modelling and
as adsorbent and inert component (solvent), respectively. simulation of kinetics of adsorption of single xylene solu-
The micropore diffusion is rate-controlling mechanism tion, taking into the consideration the micropore (crystal)
from 9 to 20
C; at 20
C both micropore and macropore diffusion.

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676 MINCEVA and RODRIGUES

Figure 10. o-Xylene uptake curves (experimental and simulated with macropore diffusion model) at (a) 50
C (j, experiment 11); (b) 80
C (j, experiment
13; D, experiment 12); (c) 120
C (j, experiment 15; D, experiment 14); (d) 180
C (j, experiment 16).

Macropore–Micropore Diffusion Model Initial and boundary conditions

The model assumptions are the same as for the macropore
diffusion model except assumption (4), which is replaced q(r, R, 0) ¼ 0 0  r  rc t > 0 (21)
with ‘macropore and micropore diffusion mechanisms are qm bcp (R, t)
in series and control the rate of adsorption’. As mentioned q(rc , R, t) ¼ t>0 (22)
1 þ bcp (R, t)
before the pore size of the crystals is of the order of
the molecular dimensions, and, therefore, molecules inside @q
(0, R, t) ¼ 0 t>0 (23)
the crystals never escape the attraction potential of the pore @r
walls. For example, the kinetic diameter of p-xylene is
6.7 Å, that of o-xylene is 7.4 Å and for i-octane 6.7 Å. where r is the radial distance from the center of the crystal; t
On the other hand, the effective micropore size of NaX is is the time; q is adsorbed phase concentration; rc is the
8.4 Å, KBaY 8.0 Å and NaY 8.0 Å (Moya-Korchi, 1995). crystal radius; and Dc is micropore (crystal) or transport
Therefore the diffusion mechanism in the microparticle diffusivity.
(crystals) is assumed to be the hopping process of the The micropore diffusion is a function of the adsorbent
molecules from one low energy position to the next low loading and the temperature. In the case of Langmuir
energy position within the microparticle. isotherm the following correlation is applied (Do, 1998):

D0c
Dc ¼
(1  y)


Model Equations E
D0c ¼ D0c1 exp (24)
Mass balance in the crystal RT

where D0c is the corrected diffusivity in the micropore; D0c1

  is the corrected diffusivity in the micropore at infinite
@q 1 @ 2 @q
¼ 2 r Dc 0  r  rc t>0 (20) temperature; E is activation energy for the micropore diffu-
@t r @r @r sion and y is the adsorbent loading (q=qm).

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 ADSORPTION OF XYLENES 677

Figure 11. Ethylbenzene uptake curves (experimental and simulated with macropore diffusion model) at (a) 50
C (j, experiment 18); (b) 80
C
(j, experiment 19); (c) 120
C (j, experiment 20); (d) 180
C (j, experiment 21).

Mass balance in the volume element of the pellet Initial condition

 
@cp @
q 1 @ 2
@cp c(0) ¼ c0 (31)
ep þ rp ¼ 2 D R
@t @t Rp @R p @R c0 is bulk phase initial concentration (mol dm ). 3

0  R  Rp t>0
(25) Numerical solution of model equations
Model equations [equations (20)–(31)] were numerically
The average adsorbed phase concentration in the crystal (
q) solved by gPROMS. The orthogonal collocation method of
for an arbitrary time and arbitrary radial distance, R, from finite elements was used for the discretization of the radial
the center of the pellet is calculated as: domains. Each crystal and pellet was divided into 10 and 20
ð equal elements, respectively, with two collocation points in
3 rc
q
(R, t) ¼ 3 q(r, t)r2 dr (26) each element. For a typical simulation, a CPU time of about
rc 0 10 s is required with a Pentium III 726 MHz processor.

Initial and boundary conditions Simulation results

The model parameters used in the simulation of each
cp (R, 0) ¼ 0 0  R  Rp (27) uptake experiment are given in Table 5, the isotherm
@cp parameters are presented in Table 3 and adsorbent properties
(0, t) ¼ 0 t>0 (28) in Table 2.
@R
The p-xylene, o-xylene and ethylbenzene uptake curves
cp (Rp , t) ¼ c(t) t>0 (29) calculated using the macropore–micropore model are
presented in Figure 12(a–c), respectively. The macropore–
micropore model describes satisfactorily the uptake curves at
Mass balance in the bulk liquid phase low temperatures. There is relatively small deviation of the

  experimental data from the simulated uptake curves. One of
dc 1e 3 @cp 
¼ D  (30) the possible reasons could be the size of the adsorbent pellets,
dt e Rp p @R R¼Rp
namely the size of the pellets varies between 0.3 and 1 mm

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678 MINCEVA and RODRIGUES

Figure 12. Uptake curves (experimental and simulated with macropore-micropore diffusion model) at (a) p-xylene at 30
C (j, experiment 1) and at 50
C (j,
experiment 2); (b) o-xylene at 30
C (j, experiment 10); (c) ethylbenzene at 30
C (j, experiment 17).

(diameter) and in the model all particles are assumed with a faujasite type of zeolites is presented in Table 6. The activa-
constant size 0.62 mm, obtained from the particle size distri- tion energy for the p-xylene micropore-corrected diffusivity is
bution analysis. The size of the microcrystals was assumed to in the range of values obtained by other researchers. The
be 1 mm in diameter. The value of the corrected diffusivity in corrected diffusivity in the micropore is smaller compared
the micropore (D0c ) which best fit the experimental data is in with the data presented in Table 6. This could be due to the
order 1015–1014 cm2 s1 (Table 5). The order of corrected type of the solvent used, the size of the crystals or the size of
micropore diffusion at 30
C is ethylbenzene (4.5 the molecules of the aromatic hydrocarbon components.
1014 cm2 s1) > o-xylene (1.5  1014 cm2 s1) > p-xylene
(8  1015 cm2 s1). The micropore diffusivity (Dc) changes
from 1014 to 1010 cm2 s1 with increase in the adsorbent
coverage from 0 to 1 (Figure 13). The activation energy for
the corrected diffusivity in the micropore for p-xylene was
calculated using the equation (24) and p-xylene corrected
diffusion values at 30 and 50
C. The activation energy for the
micropore corrected diffusivity was 41.6 kJ mol1. This value
was used to calculate the corrected diffusion in micropore
(D0c ) for p-xylene at 80
C (D0c ¼ 1:08  1013 cm2 s1 ). The
p-xylene uptake curve was then simulated using the macro-
pore–micropore diffusion model. The difference between the
uptake curve simulated by macropore and macropore–
micropore model was insignificant. This agrees with the
previous conclusion that the kinetics of p-xylene adsorption
above 80
C is controlled by diffusion in the macropore. The
summary of the micropore (crystal) diffusion and activation Figure 13. The micropore diffusion vs. adsorbent loading for: (s) p-xylene;
energy for adsorption of some aromatic hydrocarbons on (j) ethylbenzene; (D) o-xylene at 30
C.

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 ADSORPTION OF XYLENES 679

CONCLUSIONS
The equilibrium and kinetics of adsorption of p-xylene,
o-xylene and ethylbenzene on Ba-exchanged faujasite type
of zeolite were studied in a liquid phase at temperatures
between 30 and 180
C. The equilibrium of adsorption was
described by Langmuir and Sips isotherm. The Sips equation
fits better the equilibrium experimental data than the Lang-
muir isotherm. The saturation capacity of the adsorbent is
similar for all components and comparable to typical values
for ion-exchanged faujasite zeolites found in the literature.
The values of the isosteric heat of adsorption are in order
p-xylene(27.2 kJ mol1) > ethylbenzene(20.3 kJ mol1) > o-
xylene(18.6 kJ mol1).
The study of kinetics of adsorption has shown that the
macropore diffusion is the rate-controlling mechanism at
temperatures between 180 and 80
C for p-xylene and
between 180 and 50
C for o-xylene and ethylbenzene.
The micropore diffusion contributes to the control of the
adsorption rate at lower temperatures. The micropore-
corrected diffusion in the crystals is in order 1015–
1014 cm2 s1 and the activation energy for the micropore
corrected diffusion is 41.6 kJ mol1.
and
kf Rp
Bi ¼
Dp
The boundary condition at the particle surface becomes:

@c  
 ¼ Bi(c  cp x¼1 )
@x x¼1
The method of Li et al. (2003) has been applied for the
uptake curve of p-xylene at 120
C in order to ensure that
micropore diffusion does not contribute in the control of the
kinetics of adsorption. The experimental uptake curve as a
function of time (t) and simulation uptake curves for
different values of Bi as a function of dimensionless time
(t) are presented in Figure A1(a) and (b), respectively.
According to the method, the real time t and dimensionless
time t were read for each experimental value of the bulk
concentration; and t  t curves for various Bi have been
plotted (Figure A1c).
The Bi value used (Bi ¼ 100) to simulate the experimental
p-xylene uptake curve leads to straight line t  t, which
means that the external mass transfer is negligible.

APPENDIX: DETERMINATION OF THE INFLUENCE NOMENCLATURE

OF THE EXTERNAL MASS TRANSFER b affinity or Langmuir constant, m3 mol1
bs parameter in Sips equation, m3 mol1
Li et al. (2003) proposed a method for calculation of the b1 pre-exponential factor in constant b of Langmuir isotherm,
external (film) mass transfer and effective pore diffusivity m3 mol1
from the batch uptake experiments. It also provides a way of bs1 adsorption affinity constant at infinite temperature in Sips
checking if external mass transfer is negligible. In order to equation, m3 mol1
apply this method the external mass transfer has been cp fluid phase concentration in the macropores, mol m3
c* equilibrium liquid phase concentration, mol m3
included into the macropore diffusion model [equations c bulk fluid phase concentration, mol m3
(10)–(19)]. The boundary condition at the particle surface c0 bulk fluid phase initial concentration, mol m3
[equation (13)] has been replaced with: D0AB diffusion coefficient of solute A at very low concentrations in
 solvent B, m2 s1
@cp   Dc transport or micropore (crystal) diffusivity, m2 s1
Dp  ¼ kf (c  cp R¼R )

@R R¼Rp p D0c corrected diffusivity in micropore, m2 s1
D0c1 corrected diffusivity in micropore at infinite temperature,
m2 s1
where kf (m s1) is the external mass transfer coefficient. Dp pore diffusivity, m2 s1
Dimensionless variables introduced in the macropore E activation energy for the corrected diffusivity in micropore,
diffusion model are: J mol1
MB molecular weight of solvent B, kg mol1
Dp n Sips equation parameter
t¼ 2t N number of the experiments
Rp DH isosteric heat of adsorption, J mol1
R r radial distance from the canter of the crystal, m
x¼ R radial distance from the canter of the pellet, m
Rp R gas constantin in equations (2), (4), (7)–(9), 24, J mol1 K1

Table 6. Literature survey on micropore diffusion and activation energy for micropore diffusion for some aromatic hydrocarbons.

Adsorbent Solvent Sorbate T,
C E, kJ mol1 Dc, cm2 s1 Reference

Ba exchanged faujasite i-Octane p-Xylene 30 41.6 8  1015 This work
pellets (Rp ¼ 0.0031 cm) o-Xylene 1.5  1014
with crystals of 1 mm Ethylbenzene 4.5  1014
NaY crystals of 1.1 mm Cyclohexane p-Xylene 25  1012 Moore and Katzer (1972)
m-Xylene  1014
Benzene 50–70
NaY crystals of 1 mm Cyclohexane Cumene 30, 50 15  1012 Satterfield and Cheng (1972b)
Trimethylbenzene 4.4  1012
NaX crystals of 20–40 mm n-Hexane o-Xylene 80 2  109 Awum et al. (1988)
Benzene 31 2  108
Cyclohexane Benzene 36 3.4  109
NaY crystals of 1 mm Thrialkylbenzene Thrialkylbenzene 30 1013 7 1012 Satterfield and Cheng (1972a)

Trans IChemE, Part A, Chemical Engineering Research and Design, 2004, 82(A5): 667–681
680 MINCEVA and RODRIGUES

Figure A1. Determination of the influence of the external mass transfer. (a) Experimental uptake curve for p-xylene at 120
C (experiment 5; u, experimental
data, ——, simulated results; Bi ¼ 100); (b) bulk concentration as a function of dimensionless time t (simulation results for different values of Bi); (c) t 7 t
curves for various Bi obtained by reading corresponding values of t and t for each experimental point of bulk concentration.

rc radius of the crystal, m Broughton, D.B., Neuzil, R.W., Pharis, J.M. and Brearley, C.S., 1970,
Rp radius of the pellet, m The parex process for recovering paraxylene, Chem Eng Prog, 66(9):
t time, s 70–75.
T temperature, K Cavalcante, C.L. Jr., Lima, V.E., Sousa, L.G. and Alsina, O.L.S., 1997,
q adsorbed concentration, mol kg1 Sorption kinetics of aromatics in Y zeolite pellets using the gravimetric
qm saturation capacity, mol kg1 method, Braz J Chem Eng, 14(3): 191–197.
qms parameter in Sips equation, mol kg1 Do, D.D., 1998, Adsorption Analysis: Equlibria and Kinetics, Series on
q* equilibrium adsorbed concentration, mol kg1 Chemical Engineering, Vol 2, Yang, R.T. (ed.) (Imperial College Press,
qcal
* calculated equilibrium adsorbed concentration, mol kg1 London, UK).
qexp
* experimental equilibrium adsorbed concentration, mol kg1 Fabri, J. and Veba, A.G., 2002, Production, separation, and further proces-

q average adsorbed phase concentration, mol kg1 sing, in Ullmann’s Encyclopedia of Industrial Chemistry, electronic
Q heat of the adsorption, J mol1 version (Wiley-VCH, Berlin, Germany).
Qy¼0:5 isosteric heat at the fractional loading of 0.5 in equation (9), Furlan, L.T., Chaves, B.C. and Santana, C.C., 1992, Separation of liquid
J mol1 mixtures of p-xylene and o-xylene in X zeolites: the role of water content
VA molar volume of solute A at its normal boiling temperature, on the adsorbent selectivity, Ind Eng Chem Res, 31(7): 1780–1784.
m3 mol1 Hsiao, H.S., Yih, S.M. and Li, M.H., 1989, Adsorption equilibrium of
Vl volume of the liquid phase, m3 xylene isomers and p-diethylbenzene in the liquid phase on a Y zeolite,
Vp volume of the adsorbent pellets, m3 Adsorp Sci Technol, 6(2): 64–82.
Li, P., Xiu, G. and Rodrigues, A.E., 2003, Modelling separation of proteins
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ACKNOWLEDGMENTS
One of us (Mirjana Minceva) gratefully acknowledges the financial
support of ‘Fundação para a Ciencia e a Tecnologia’, grant PRAXIS
XXI=BD=19503=99. This work was financially supported by the project
POCTI=EQU=44515=2002 (‘Fundação para a Ciência e Tecnologia’).
The manuscript was received 29 September 2003 and accepted for
publication after revision 2 February 2004.