Article

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Adsorption Equilibria of Water Vapor on Zeolite 3A, Zeolite 13X, and

Dealuminated Y Zeolite
Kyung-Min Kim, Hyun-Taek Oh, Seung-Jun Lim, Keon Ho, Yongha Park, and Chang-Ha Lee*
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-Gu, Seoul, 120-749,
Republic of Korea
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ABSTRACT: The adsorption equilibria of water vapor on zeolite 3A, zeolite 13X, and dealuminated Y zeolite (DAY) were
measured using a volumetric method. Equilibrium experiments were conducted at 293.15, 303.15, and 313.15 K and at relative
pressure (P/Ps) up to 0.95. Experimental data were correlated using Aranovich−Donohue and Frenkel−Halsey−Hill models,
using Langmuir, Toth, UNILAN, and Sips isotherms.

1. INTRODUCTION swing adsorption and pressure swing adsorption processes over

In various industrial processes, many effluent gases contain some
water vapor. For example, in petrochemical processes such as
steam cracking, steam reforming, and water gas shift reaction,
water is injected or is generated during the reaction. The effluent
gases from iron/steel processing, coal gasification, olefin/paraffin
processing, and so forth, also include water vapor. In particular,
natural gas is typically saturated with water vapor under normal
production conditions.
In gas separation, water vapor is the most common undesir-
able impurity to be removed from the desirable component
of effluent gas mixtures. Furthermore, water removal is crucial
in air dryer and air separation process. Accordingly, the
dehydration process is generally carried out in a pretreatment
unit to avoid unexpected side effects during further processing.
Water removal from gas streams reduces the potential for
undesirable effects, such as corrosion in the presence of acid
contaminants, hydrate formation, hydrolysis reaction with the
fluid itself, and condensation or freezing of moisture.1,2 In
addition, because water vapor can act as a catalyst poison or a
source of undesirable side reactions, gas streams are occasion-
ally dehydrated in catalytic processes.3−5
The demands for moisture removal have continuously
increased along with the increasing stringency of requirements
for product quality control and production energy efficiency.6
Therefore, various dehydration methods are used in industrial
practice, such as adsorption, absorption, and compression. Among
them, adsorption is known as the most efficient method.1,2,7
Moisture removal can be carried out by means of temperature
a wide range of operating conditions.1,8−10
Because adsorption is purely a surface phenomenon and the
degree of adsorption is a function of temperature and pressure,
the adsorption equilibrium of water vapor is essential in sel-
ecting the proper adsorbent and designing an efficient adsorp-
tion process.8,10,11 Zeolites are widely applied for adsorptive
dehydration processes when gases having extremely low dew
points are required for further processing. On the other hand,
for purification of adsorptive waste gas and recovery of volatile
organic compounds, highly dealuminated Y zeolite (DAY) is
often selected as the adsorbent because of its hydrophobicity
and relatively high ignition resistance.
This study presents adsorption equilibria of water vapor
on zeolite 3A, zeolite 13X, and dealuminated Y zeolite (DAY).
Because pellet- or bead-type adsorbents are generally applied
to adsorptive packed beds for dehydration, zeolite pellets, or
beads were studied. Equilibrium experiments were performed
at 293.15, 303.15, and 313.15 K and at relative pressures
up to P/Ps = 0.95 (2.2, 4.0, and 7.0 kPa, respectively). The
experimental data obtained were correlated using the
Aranovich−Donohue (AD) and Frenkel−Halsey−Hill (FHH)
models.
Received: November 2, 2015
Accepted: March 1, 2016
Published: March 11, 2016

© 2016 American Chemical Society 1547 DOI: 10.1021/acs.jced.5b00927

J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data Article

2. EXPERIMENTAL SECTION 3. RESULTS AND DISCUSSION

Materials. Three different types of zeolite pellets or beads Adsorption Isotherm. Adsorption isotherm data of water
were selected: zeolite 3A (EPG MOLSIV, UOP, USA), zeolite vapor on zeolite 3A, zeolite 13X, and DAY at 293.15, 303.15,
13X (APG MOLSIV, UOP, USA), and DAY (DAY 20F, and 313.15 K are plotted in Figures 1−3, and the experimental
20:1 Si:Al ratio, Degussa AG, Hanau, Germany). Table 1 lists the

Table 1. Physical Properties of Zeolite 3A, Zeolite 13X, and

DAY
property Zeolite 13X Zeolite 3A DAY
type bead pellet pellet
bulk density/kg·m−3 640 660 500
BET surface area/m2·g−1 743a 704b
micropore volume/cm3·g−1 0.3964a 0.268b
micropore size/Åc 8−9 3 7.4
particle size/mm 2.1 3.7 2
average pore diameter/nm 1.79a 2.17b
total porosityd 0.2923 0.4219 0.4342
a
Data obtained by CO2 adsorption and desorption isotherm. bData
obtained by N2 adsorption and desorption isotherm. cReferences 12
and 13. dData obtained by measuring mercury porosimeter.
Figure 1. Experimental and correlated isotherms for water vapor on
Zeolite 3A at various temperatures (triangle up: 293.15 K, circle:
physical properties of zeolite 3A, zeolite 13X, and DAY. Water 303.15 K, square: 313.15 K, filled triangle up: 298.15 K at zeolite 5A,
used in the experiments was double-distilled water treated by an filled square: 323.15 K at zeolite 5A (Y. Wang et al. 2009), solid lines:
evaporator and deionizer with ion-exchange resin. AD with Toth, dash lines: AD with Langmuir, dash-dot lines: AD with
Apparatus. Experiments to determine adsorption equilibria Sips, dotted lines: Sips).
were conducted using an automatic volumetric sorption
analyzer (Quantachrome, ASIQM0 V000-4) with a vapor
sorption unit. The vapor unit consists of a manifold heater and
circulation fan inside the insulated manifold compartment, plus
a vapor generator and control. The vapor generator consists of
a glass vial, similar to a small Erlenmeyer flask, approximately
5 cm long. The liquid (vapor source) is held in the vial, and the
stem portion of the vial attaches to the vacuum-tight fitting
behind the access. The generated vapor is supplied to the
volumetric sorption analyzer without any condensation. Prior
to each experiment, about 0.1 g of the relevant adsorbent was
placed into an adsorption cell. In the method used, the total
amount of gas admitted into the system and the amount of gas
in the vapor phase, remaining after reaching the adsorption
equilibrium, were determined from the results of appropriate
P−V−T measurements.
Procedure. All adsorbents were kept in dried vials at room Figure 2. Experimental and correlated isotherms for water vapor on
temperature. After thermal regeneration (573.15 K) under Zeolite 13X at various temperatures (triangle up: 293.15 K, circle:
303.15 K, square: 313.15 K, solid lines: AD with Toth, dash lines: AD
vacuum, the mass of each adsorbent sample was measured using
with Langmuir, dash−dot lines: AD with Sips, dotted lines: Sips; filled
a microbalance with an accuracy of ±100 μg. To eliminate triangle up: 298.15 K (Wang et al., 2009), filled circle: 293.15 K and
moisture and pollutants adsorbed during the installation of the filled square: 313.15 K (Kim et al., 2003).
adsorption cell, the adsorbents were the regenerated again at
573.15 K under high vacuum for 12 h. Then, the adsorption cell
was placed in a water bath and maintained at a constant data are presented in Tables 2−4. Experimental reproducibility
temperature within ±0.05 K by a water circulator (type RW, within 3% was confirmed by means of duplicate experiments.
Jeio Tech Co.). To keep the water vapor from condensation in The trend in water adsorption on the three zeolites was zeolite
the system, the temperature of the manifold in the system was 13X > zeolite 3A > DAY for all pressure and temperature
maintained over 318.15 K by a heater. The maximum experi- conditions tested.
mental pressure was limited to remain at or below the point At all temperatures, the adsorption isotherms of zeolite 3A
where the relative pressure of water vapor at each temperature and zeolite 13X were classified as Type II in the BDDT classifi-
was 0.95. The saturated vapor pressure was calculated by using cation (Figures 1 and 2). Each adsorption isotherm indicated
the Antoine equation with the parameters obtained from the noticeable uptakes at very low pressure region. They showed
Dortmund Data Bank (DDBST) Web site. The saturated vapor multilayer adsorption and condensation near the relative
pressures were 2.3295, 4.2316, and 7.3585 kPa at 293.15, 303.15, pressures P/PS of 0.87 and 0.90 on zeolite 3A and zeolite
and 313.15 K, respectively. Thus, the respective maximum 13X, respectively. Monolayer coverage was completed at a very
experimental pressures were set to 2.2, 4.0, and 7.0 kPa, low pressure, showing very high adsorption affinity, and the first
according to the maximum of P/Ps = 0.95. isotherm inflection was observed near P/PS of 0.18 for both
1548 DOI: 10.1021/acs.jced.5b00927
J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data Article

below 0.65. Then, the adsorbed moles were steeply increased

Figure 3. Experimental and correlated isotherms for water vapor on
DAY at various temperatures (triangle up: 293.15 K, circle: 303.15 K,
square: 313.15 K, solid lines: AD with Toth, dash lines: AD with
Langmuir, dash−dot lines: AD with Sips; plus sign: 293.15 K and X
sign: 313.15 K (Kim et al., 2005).
zeolite 3A and zeolite 13X. The adsorption isotherms of DAY
showed type III of a convex shape in Figure 3. After an
indistinct inflection near P/PS = 0.01, the adsorbed amount
of water was almost linearly increased with a relative pressure
by multilayer adsorption and condensation.
The adsorbed amount of water and the affinity of water on
zeolite 13X were higher than those of water on zeolite 3A at
each temperature condition tested (Figures 1 and 2, insets).
In the pressure range of 0.1−0.7 kPa, the adsorbed amount of
water on zeolite 13X at 313.15 K was actually also larger than
that on zeolite 3A at 293.15 K. The adsorbed amount on DAY
was much smaller than that on the other two zeolites because of
its hydrophobicity (Figure 3).
The experimental results on zeolite 13X at 293.15 and
313.15 K were compared with published results;14,15 the shape
of the isotherm of zeolite 13X at 293.15 K was similar to that of
the reference, but the adsorbed amount observed in the present
study was higher than that of the reference (Figure 2). As listed
in Table 1, the surface area (726 m2·g−1) and particle density
(0.69 g·cm−2) differed somewhat from the reference values.
The experimental data of zeolite 3A was compared with the
previously reported data of zeolite 5A15 because it was hard to
find any reported data of zeolite 3A. The adsorption capacity of
zeolite 5A was higher than that of zeolite 3A. The experimental
results on DAY at 293.15 and 313.15 K were also compared
with the results of a previous study;16 the adsorbed amount in
the present study was less than the reference value, and the

Table 2. Experimental Adsorption Isotherm Data for Water Vapor on Zeolite 3Aa
P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1
293.15 K
0.003 0.043 0.043 7.923 0.473 9.876 1.637 11.27
0.004 0.899 0.063 8.394 0.583 10.09 1.740 11.39
0.006 1.813 0.084 8.652 0.704 10.29 1.863 11.57
0.008 3.065 0.113 8.796 0.815 10.45 1.986 11.85
0.011 5.959 0.134 8.905 0.949 10.61 2.102 12.39
0.013 6.741 0.157 9.018 1.055 10.74 2.118 12.54
0.015 7.030 0.183 9.133 1.171 10.85 2.141 12.73
0.017 7.212 0.205 9.223 1.286 10.95 2.167 12.97
0.019 7.340 0.229 9.314 1.399 11.04 2.185 13.16
0.021 7.449 0.346 9.602 1.520 11.16 2.211 13.45
303.15 K
0.005 0.001 0.080 7.810 0.853 9.270 2.967 10.48
0.008 0.363 0.115 7.985 1.085 9.455 3.180 10.66
0.014 0.992 0.162 8.213 1.263 9.568 3.387 10.85
0.017 1.735 0.204 8.353 1.480 9.694 3.605 11.15
0.021 2.563 0.247 8.464 1.684 9.814 3.839 11.75
0.026 3.442 0.285 8.552 1.915 9.935 3.857 11.87
0.028 4.733 0.332 8.640 2.120 10.03 3.893 12.03
0.031 6.678 0.377 8.726 2.320 10.13 3.944 12.24
0.034 7.145 0.419 8.789 2.558 10.23 3.994 12.49
0.038 7.364 0.646 9.071 2.760 10.35 4.018 12.70
313.15 K
0.008 0.196 0.139 7.608 1.489 9.161 5.165 10.40
0.014 0.637 0.199 7.867 1.870 9.332 5.703 10.61
0.020 1.311 0.277 8.075 2.224 9.467 6.286 10.85
0.028 2.245 0.356 8.234 2.560 9.577 6.644 11.22
0.037 3.275 0.433 8.356 2.984 9.711 6.693 11.33
0.041 4.264 0.500 8.447 3.328 9.810 6.768 11.52
0.047 5.509 0.577 8.538 3.702 9.914 6.851 11.71
0.056 6.663 0.658 8.625 4.038 10.02 6.918 11.90
0.066 6.939 0.723 8.689 4.421 10.13 6.990 12.09
0.069 7.197 1.150 8.983 4.817 10.27

a
Uncertainties: ΔT = 0.05 K, P/Ps < 0.001.

1549 DOI: 10.1021/acs.jced.5b00927

J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data Article

Table 3. Experimental Adsorption Isotherm Data for Water Vapor on Zeolite 13Xa
P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1
293.15 K
0.003 0.023 0.044 12.04 0.470 14.90 1.625 16.80
0.004 1.763 0.065 12.53 0.583 15.17 1.744 16.99
0.006 5.383 0.087 12.87 0.705 15.43 1.863 17.22
0.009 6.316 0.114 13.05 0.823 15.64 1.978 17.50
0.011 7.257 0.138 13.39 0.929 15.82 2.100 17.97
0.013 8.200 0.157 13.57 1.052 16.00 2.118 18.09
0.015 9.125 0.182 13.75 1.159 16.15 2.138 18.25
0.018 10.47 0.203 13.90 1.287 16.33 2.164 18.44
0.019 11.04 0.228 14.04 1.401 16.48 2.186 18.63
0.021 11.26 0.355 14.55 1.522 16.65 2.208 18.86
303.15 K
0.005 0.014 0.165 12.73 1.282 15.26 3.394 16.89
0.012 1.493 0.204 13.00 1.503 15.46 3.601 17.13
0.018 3.276 0.243 13.23 1.698 15.63 3.822 17.47
0.026 5.734 0.290 13.45 1.920 15.80 3.852 17.57
0.029 7.707 0.332 13.62 2.138 15.96 3.894 17.67
0.032 9.213 0.371 13.76 2.329 16.09 3.936 17.76
0.036 10.31 0.415 13.90 2.558 16.25 3.977 17.90
0.038 10.89 0.632 14.38 2.771 16.40 4.017 18.04
0.077 11.82 0.876 14.77 2.972 16.54
0.114 12.27 1.065 15.01 3.170 16.70
313.15 K
0.009 0.631 0.125 11.37 1.454 14.50 5.159 16.23
0.014 1.887 0.224 12.15 1.835 14.77 5.521 16.37
0.023 3.615 0.273 12.45 2.252 15.02 5.881 16.51
0.027 5.362 0.348 12.75 2.606 15.21 6.283 16.70
0.037 7.291 0.441 13.05 2.991 15.40 6.643 16.88
0.041 8.686 0.501 13.22 3.307 15.53 6.696 16.94
0.048 9.686 0.573 13.39 3.669 15.67 6.775 16.99
0.057 10.30 0.654 13.56 4.038 15.81 6.884 17.10
0.061 10.58 0.717 13.68 4.420 15.95 6.934 17.12
0.068 10.74 1.122 14.20 4.792 16.09 7.022 17.40
a
Uncertainties: ΔT = 0.05 K, P/Ps < 0.001.

isotherm shape was also quite different from that of the reference where q is the number of adsorbed molecules in moles, and the
isotherm, which was nearly linear. Because of this difference, term 1/(1−P/PS)d describes the divergence of q under pres-
the isotherms were measured repeatedly and confirmed to sure approaching saturation. Given the definition of f(P), the
be reproducible within 3%. It is expected that the observed monolayer capacity qm can be determined from f(PS) because
difference in isotherms arose from differences in the properties f(PS) corresponds to the maximum monolayer adsorption.
of adsorbents manufactured by different companies, because the The following Langmuir, Toth, UNILAN, and Sips equations
crystal size and the binder type can be different among the were used to model f(P) in eq 1.
zeolites used in the study and references. In addition, differences Langmuir isotherm model:
in the experimental method and system may have led to some
qmbP
differences in the resulting isotherms. f (P ) =
Isotherm Models. The adsorption isotherms of zeolite 3A (1 + bP) (2)
and zeolite 13X were classified as type H3 in the classification
system of Giles et al.17 In the adsorption isotherms each had an Toth isotherm model:
inflection point at which the isotherm changed from convex to qmbP
concave (high adsorption affinity at low pressure to con- f (P ) =
densation with pressure increase; see Figures 1 and 2). On the (1 + (bP)t )1/ t (3)
other hand, the adsorption isotherms of DAY were of the UNILAN isotherm model:
L3 type. Although the L3 type is similar to the H3 type, the
slope of the L3 isotherm remained almost constant throughout qm ln⎡⎣(c + Pe+s)/(c + P e−s)⎤⎦
the low pressure region (Figure 3). f (P ) =
2s (5)
In the study, the AD and FHH models were used to correlate
the experimental data.18−20 Sips isotherm model:
The AD equation is as follows:
qm(bP)1/ n
f (P ) =
q = f (P)/(1 − P /PS)d (1) 1 + (bP)1/ n (6)

1550 DOI: 10.1021/acs.jced.5b00927

J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data Article

Table 4. Experimental Adsorption Isotherm Data for Water Vapor on DAYa

P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1 P/kPa q/mol·kg−1
293.15 K
0.004 0.010 0.042 0.116 0.466 0.370 1.635 1.749
0.005 0.026 0.068 0.143 0.576 0.434 1.741 2.213
0.006 0.037 0.090 0.162 0.705 0.514 1.862 3.145
0.009 0.052 0.114 0.179 0.822 0.595 1.975 4.860
0.011 0.061 0.137 0.194 0.938 0.683 2.092 7.677
0.013 0.070 0.162 0.210 1.063 0.792 2.115 8.623
0.015 0.076 0.186 0.225 1.163 0.896 2.139 9.609
0.017 0.082 0.206 0.237 1.286 1.045 2.167 10.61
0.019 0.086 0.227 0.249 1.404 1.221 2.188 11.59
0.022 0.089 0.353 0.310 1.518 1.435 2.208 12.36
303.15 K
0.005 0.001 0.121 0.152 1.084 0.438 3.171 2.069
0.008 0.041 0.168 0.173 1.272 0.494 3.381 2.875
0.017 0.067 0.202 0.187 1.496 0.568 3.600 4.438
0.019 0.075 0.242 0.201 1.707 0.643 3.818 7.382
0.023 0.081 0.285 0.216 1.908 0.733 3.847 8.115
0.027 0.088 0.330 0.229 2.132 0.845 3.896 8.697
0.031 0.093 0.370 0.242 2.351 0.989 3.952 9.462
0.037 0.100 0.415 0.256 2.551 1.147 3.979 10.50
0.042 0.105 0.645 0.314 2.754 1.352 4.018 11.25
0.082 0.133 0.869 0.376 2.959 1.610
313.15 K
0.008 0.001 0.211 0.12 1.854 0.398 5.523 2.087
0.022 0.036 0.292 0.141 2.192 0.463 5.887 2.914
0.023 0.036 0.358 0.155 2.585 0.535 6.261 4.363
0.038 0.046 0.428 0.170 2.984 0.624 6.619 6.246
0.043 0.048 0.504 0.185 3.334 0.712 6.743 7.390
0.048 0.051 0.583 0.198 3.732 0.844 6.775 7.607
0.056 0.057 0.656 0.212 4.072 0.975 6.839 8.058
0.061 0.060 0.731 0.224 4.468 1.158 6.921 9.400
0.069 0.066 1.112 0.283 4.776 1.350 6.994 10.56
0.140 0.097 1.505 0.341 5.169 1.675
a
Uncertainties: ΔT = 0.05 K, P/Ps < 0.001.

Here, qm, b, t, c, s, n, A, B, and d are isotherm parameters that where k is the number of data points at a given temperature,
are numerically determined. In addition, adsorption isotherm and where qexp and qcal refer to experimentally observed and
data in the low pressure range (up to P/PS = 0.3) were correlated calculated numbers of adsorbed moles, respectively.
using the Sips isotherm model given in eq 6. The adsorbed moles at very low relative pressures were
The FHH equation was originally developed by assuming that commonly very small; hence these experimental data definitely
the adsorption potential varies with distance from the surface.19 had much greater deviations than others measured at higher
The FHH equation can describe the range of multilayer relative pressures. As a result, deviation calculations including
adsorption on a homogeneous planar surface and is attractive for all experimental points could lead to some skewed results due
its simple mathematical form: to the inclusion of these data. For an example, using the AD
⎛P⎞ equation with the Sips isotherm yielded a calculation of
ln⎜ ⎟ = − A(q)−B 327% average deviation from experimental data on zeolite 3A at
⎝ PS ⎠ (7)
Table 5. AD Equation Parameters for Water Vapor on
The parameter B is regarded as a standard of the rate of Zeolite 3A, Zeolite 13X, and DAY for f(P) = Langmuir
decline in the adsorption potential with distance from the Equation
surface. B is usually less than 3, and it is assumed that observed
deviations from the theoretical value arise from the roughness adsorbent T/K qm/mol·kg−1 b/kPa d Δq/%
of a real adsorbent surface. Zeolite 3A 293.15 10.25 61.56 0.08859 5.36
The fitting of the models to experimental data was performed 303.15 9.5 33.01 0.09621 4.45
using Matlab 7.10 software (Mathworks, Inc.), using a nonlinear 313.15 9.326 20.93 0.08936 3.67
curve fitting procedure. In this study, the average percent Zeolite 13X 293.15 15.45 63.63 0.07048 4.31
deviation (Δq) was calculated using the following equations: 303.15 15.5 26.93 0.05668 3.96
313.15 15.13 18.47 0.0514 5.3
100
k qjexp − qjcal DAY 293.15 0.564 2.742 1.097 21.58
Δq = ∑
k j=1
qjexp 303.15 0.4872 2.3 1.101 17.94
(8) 313.15 0.4412 1.284 1.108 15.56

1551 DOI: 10.1021/acs.jced.5b00927

J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data Article

Table 6. AD Equation Parameters for Water Vapor on Zeolite 3A, Zeolite 13X, and DAY for f(P) = Toth Equation
adsorbent T/K qm/mol·kg−1 b/kPa t d Δq/%
Zeolite 3A 293.15 11.24 3641 0.3836 0.0826 1.22
303.15 10.04 2837 0.4031 0.09479 4.74
313.15 10.4 2371 0.36 0.07506 2.57
Zeolite 13X 293.15 19.43 9.35 × 104 0.2472 0.05246 2.58
303.15 18.64 8415 0.2938 0.04113 1.52
313.15 19.06 1.11 × 104 0.2652 0.02983 1.64
DAY 293.15 6.591 11.18 0.1801 1.05 10.33
303.15 10.1 27.88 0.1404 1.042 9.46
313.15 31.62 9.198 0.117 1.012 5.03

Table 7. AD Equation Parameters for Water Vapor on Zeolite 3A, Zeolite 13X, and DAY for f(P) = UNILAN Equation
adsorbent T/K qm/mol·kg−1 c/kPa s D Δq/%
Zeolite 3A 293.15 20.27 0.9465 15.25 0.06952 1.4
303.15 18.16 0.9881 18.12 0.0823 5.83
313.15 17.48 0.9816 14.61 0.06074 3.43
Zeolite 13X 293.15 29.04 0.4078 13.25 0.04414 3.26
303.15 30.16 1.277 12.63 0.02864 2.13
313.15 26.76 0.6102 11.33 0.01895 2.1
DAY 293.15 1.687 29.2 6.505 1.078 14.7
303.15 1.979 736.5 9.899 1.079 11.36
313.15 2.233 3124 10.16 1.067 10.16

Table 8. AD Equation Parameters for Water Vapor on Zeolite 3A, Zeolite 13X, and DAY for f(P) = Sips Equation
adsorbent T/K qm/mol·kg−1 b/kPa n d Δq/%
Zeolite 3A 293.15 10.92 172.1 2.083 0.0829 1.41
303.15 9.802 147.9 1.948 0.09637 4.55
313.15 10.26 82.75 2.434 0.07548 2.6
Zeolite 13X 293.15 16.01 102 1.557 0.06618 2.22
303.15 16.62 54.62 1.894 0.04752 1.61
313.15 19.74 23.59 3.526 0.0258 1.6
DAY 293.15 3.514 0.01194 2.182 1.049 6.57
303.15 2.446 0.01113 2.353 1.047 6.4
313.15 1.61 0.03329 1.9 1.023 4.55

Table 9. FHH Equation Parameters for Water Vapor on Table 10. Sips Equation Parameters for Water Vapor on
Zeolite 3A, Zeolite 13X, and DAY Zeolite 3A, Zeolite 13X, and DAY at Relative Pressure
(P/PS) up to 0.3
adsorbent T/K A/mol·kg−1 B/kPa Δq/%
Zeolite 3A 293.15 4.47 × 1010 10.56 5.38 adsorbent T/K qm/mol·kg−1 b/kPa n Δq/%
303.15 1.49 × 1010 10.39 8.75 Zeolite 3A 293.15 15.64 28.6 4.757 1.46
313.15 2.98 × 109 9.8 7.28 303.15 9.153 50.1 0.802 8.32
Zeolite 13X 293.15 1.48 × 1013 11.15 9.49 313.15 8.786 28.71 0.706 4.99
303.15 8.92 × 1010 9.287 8.45 Zeolite 13X 293.15 18.06 124.7 2.633 4.37
313.15 1.50 × 1012 10.53 9.1 303.15 15.31 40.11 1.215 3.89
DAY 293.15 0.6144 0.9704 14.39 313.15 15.05 30.05 1.256 4.26
303.15 0.6136 0.9806 9.03 DAY 293.15 42.88 4.47 × 10−4 1.803 10.08
313.15 0.5208 0.9682 19 303.15 41.76 1.55 × 10−4 1.919 9.89
313.15 28.78 3.75 × 10−4 1.705 5.05
293.15 K, due to the initial few data in the very low pressure
range, even though the model showed good agreement with the the insets of Figures 1−3. Overall, the AD equation with the
experimental data overall (Figure 2). Therefore, in the present Sips isotherm provided better fits than the other models, but
study, the first three experimental points corresponding to the difference in deviation among the models was not signifi-
the lowest pressures tested were excluded from the deviation cant and the steep slope of the isotherm in the low pressure
calculation. regions of the zeolite 3A and 13X (H3 type) isotherms was also
Tables 5−10 summarize the model parameters. Correlated predicted well.
results from the AD equation, used with the Sips isotherm, the Isosteric Heat of Adsorption. Temperature variation
Langmuir isotherm, and the Toth isotherm, respectively, are arising from adsorption or desorption affects adsorption
presented in Figures 1−3, and the results of the Sips monolayer dynamics in an adsorption bed regardless of the feed temp-
adsorption model at relative pressures up to 0.3 are shown in erature. Therefore, the isosteric heat of adsorption is a key
1552 DOI: 10.1021/acs.jced.5b00927
J. Chem. Eng. Data 2016, 61, 1547−1554
Journal of Chemical & Engineering Data
thermodynamic variable for designing practical gas separation
processes such as pressure swing adsorption, vacuum swing
adsorption, and temperature swing adsorption processes. In this
study, the isosteric heats of adsorption were calculated from the
temperature dependence of the equilibrium capacity by using
the Clausius−Clapeyron equation.20 The heats of adsorption
were estimated based on the isotherms at three different
temperatures. The ln p was plotted to 1/T, which was obtained
from Figures 1−3 at a fixed adsorbed amount. Then, the ΔQst
could be calculated from the slope of −ΔQst/R in a straight
fitting line:
ΔQ st ⎡ ∂ ln P ⎤
=⎢
RT 2 ⎣ ∂T ⎥⎦q (9)
where ΔQst is the isosteric heat of adsorption, P is pressure, T is
temperature, and R is the gas constant.
The isosteric heats of adsorption are presented in Figure 4.
The values of zeolites 3A and 13X were obtained from the
Figure 4. Isosteric heats of adsorption on various adsorbents with
respect to experimental data: Zeolite 3A (solid line), Zeolite 13X
(dash−dot line), and DAY (dash−dot−dot line).
linear isotherm region, showing very steep linear increase with
pressure in Figures 1 and 2, but the values of DAY were
calculated from the FHH isotherms. The isosteric heats of
adsorption varied within the range of 75 to 45 kJ·mol−1, and the
results corresponded to the range for zeolites reported in the
literature.21 The heats of adsorption followed the trend of
zeolite 3A > zeolite 13X > DAY. For all zeolites, the decrease
in the isosteric heat was observed with increasing adsorbed
amount. Therefore, the vertical interaction between water vapor
and adsorbent was dominant in the low pressure range.
Comparing the variations in the heat of adsorption among the
three zeolite materials, zeolites 3A and 13X showed steep
decrease in the heat of adsorption during initial loading. And
their heats of adsorption continuously decreased with increasing
loading amount. On the other hand, the heat of adsorption of
DAY became almost constant with increasing loading amount
after an initial decrease. This implied that condensation was
dominant after initial loading up to 4 mol·kg−1.
3. CONCLUSION
Adsorption isotherms of water vapor on zeolite 3A, zeolite 13X,
and DAY were measured by a volumetric method conducted at
293.15, 303.15, and 313.15 K and at relative pressures up to
0.95. The trend in water adsorption on the three zeolites was
1553
Article
zeolite 13X > zeolite 3A > DAY at all experimental temp-
eratures, and the trend in isosteric heats of adsorption was
zeolite 3A > zeolite 13X > DAY. The adsorption isotherms of
zeolite 3A and zeolite 13X were Type II isotherms in the BDDT
classification, and Type H3 isotherms in the classification of
Giles and co-workers. High adsorption affinity of water on zeolite
3A and zeolite 13X was observed in the low pressure range, and
completion of a monolayer and formation of a second layer
started from P/PS = 0.18. On the other hand, the DAY isotherm
was classified as Type III in the BDDT classification and Type
L2 in the classification of Giles and co-workers.
Experimental data were correlated using the AD equation
with the Langmuir, Toth, UNILAN, or Sips isotherms, and
also using the FHH equation. Among the models applied, the
AD equation with Sips isotherm yielded the best predictions
for all adsorbents. These results may be useful for designing
adsorptive dehydrogenation and/or solvent recovery processes.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +82 2 2123 2762; Fax: +82 2 312 6401. E-mail address:
leech@yonsei.ac.kr (C.H. Lee).
Funding
We would like to acknowledge the financial support from the
R&D Convergence Program of MSIP (Ministry of Science,
ICT and Future Planning) and NST (National Research
Council of Science & Technology) of Republic of Korea (CRC-
14-1-KRICT).
Notes
The authors declare no competing financial interest.
■
A
LIST OF SYMBOLS
FHH equation parameter
B FHH equation parameter
b Langmuir, Sips, and Toth isotherm parameter (kPa−1)
c UNILAN isotherm parameter (kPa)
d AD equation parameter (−)
n Sips isotherm parameter (−)
P Pressure (kPa)
Qst Isosteric heat of adsorption (kJ·mol−1)
q Adsorbed amount moles (mol·kg−1)
Δq Average percent deviation (%)
qm Langmuir, Sips, and Toth isotherm parameter (mol·kg−1)
R Ideal gas constant (J·mol−1·K−1)
T Temperature (K)
t Toth isotherm parameter (−)
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1554 DOI: 10.1021/acs.jced.5b00927

J. Chem. Eng. Data 2016, 61, 1547−1554