Chemical Engineering Science 55 (2000) 4827}4838

Sorbents for air prepuri"cation in air separation

Salil U. Rege , Ralph T. Yang *, Mark A. Buzanowski

University of Michigan, Department of Chemical Engineering, Ann Arbor, MI 48109, USA

Cosmodyne, LLC, Torrance, CA 90503-3881, USA
Received 28 January 2000; accepted 11 April 2000

Abstract

Air fed to air separation units such as cryogenic distillation columns needs to be prepuri"ed; that is, the concentration levels of
air-borne impurities such as water vapor, CO , and light hydrocarbons need to be brought down below the tolerable limits. This

process is commonly carried out by using adsorptive methods such as pressure swing adsorption (PSA) or temperature swing
adsorption (TSA). This work deals with the study of adsorption characteristics of two conventional microporous adsorbents, namely
13X zeolite molecular sieves, and activated c-Al O , and three non-conventional adsorbents, namely a natural zeolite (clinoptilolite),
 
and its K>- and Ca>-ion exchanged forms. A noteworthy feature of this work is the measurement of adsorption isotherms at very
low partial pressures of the adsorbate gas (to a few ppm). The relative merits of these adsorbents for the removal of trace amounts of
water vapor, CO , and hydrocarbons such as CH , C H , and C H are discussed. The isotherm data for 13X zeolite and c-Al O
       
has been "t to the Langmuir}Freundlich, Tòth, and Dubinin}Astakhov (DA, or potential theory) isotherm models. It has been found
that the potential theory model is the most suitable one for description of low pressure or concentration data. The origin of the better
"t by potential theory is that its corresponding energy distribution function follows a quasi-Gaussian distribution with a broadening
at high adsorption energies, and the high-energy sites are important for adsorption at low pressures or concentrations. Finally, the
possibility of using H O adsorption isotherm to evaluate the pore size distribution by the Horvàth}Kawazoe approach is

discussed.  2000 Elsevier Science Ltd. All rights reserved.

Keywords: Air puri"cation; Zeolites; Alumina; Clinoptilolite; Air-prepuri"cation; Dubinin}Astakhov equation

1. Introduction are well above the cryogenic temperatures of lique"ed

Oxygen and nitrogen are produced from atmospheric
air by either of two methods depending upon the volume
of production. For high-volume production (more than
200 tons/day), cryogenic distillation of lique"ed air is
employed, whereas for low to medium volume of produc-
tion, air separation by methods such as pressure swing
adsorption are found to be more economical (Yang,
1997). It is well known that atmospheric air contains
upto 3% of water vapor, and about 350 ppm of carbon
dioxide. Also light hydrocarbons such as methane,
ethane, ethylene and acetylene exist in traces (up to a few
ppm), especially if the air separation unit (ASU) is located
in the vicinity of another chemical manufacturing facility
or a re"nery. Since the freezing points of H O and CO
 
* Corresponding author. Tel.: #(734)-936-0771; fax: #(734)-763-
0459.
E-mail address: yang@umich.edu (R. T. Yang).
air, there is a distinct possibility of occluding distillation
column internals if the air is supplied to the cryogenic
distillation unit in its crude form. Also since a few hydro-
carbons (in particular C H , C H ) have a low solubility
   
in liquid oxygen, there is a danger of the accumulation of
the same in the reboiler of the distillation column, thus
posing an explosion hazard. In case of non-cryogenic
processes such as pressure swing adsorption (PSA), im-
purities such as water vapor and carbon dioxide are
found to adsorb strongly, and to some extent, irreversibly
on the adsorbents used for the separation of air. This
drastically a!ects the capacity as well as the selectivity of
the adsorbent for air separation. Besides, these impurities
typically have high heats of adsorption on the adsorbents
causing large temperature deviations during the adsorp-
tion and desorption steps. In extreme cases, there may
even be ice formation in the PSA bed (Collins, 1976), thus
requiring frequent plant shutdowns.
In order to prevent such malfunctions in the air separ-
ation units (ASU), it is critical to pretreat the feed air and

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 2 2 - 6
4828 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
reduce the impurity content to tolerable levels. In fact,
there were industrial accidents caused by the buildup of
airborne contaminants in cryogenic ASUs (see, for
example, C & E News, June 29, 1998, p. 18) which high-
lights the importance of this operation. The typical speci-
"cations for water vapor and carbon dioxide levels in the
ASU compressed feed air are 0.1 parts per million (ppm)
and 1.0 ppm, respectively (Jain, 1993), while those for
hydrocarbons are of the order of a few parts per billion
(ppb). The operation designed to reduce the concentra-
tion of impurities such as water vapor, carbon dioxide,
and hydrocarbons from air fed to processes such as
air-separation to required tolerable limits is commonly
termed as `air prepuri"cationa.
Several processes have been used to prepurify the feed
air in the past. One of the earliest approaches used
reversing heat exchangers, which alternately cooled the
compressed air to freeze out the water vapor and carbon
dioxide, and then evaporated the impurities by passing
hot regeneration or purge gas through the exchanger
channels. The disadvantages of this technique were the
requirement of a large amount of regeneration gas, mech-
anical problems associated with the cyclic heating and
cooling of the exchanger, and the inability of the
system to trap the hydrocarbon impurity. In recent times,
adsorptive methods such as temperature swing adsorp-
tion (TSA) and pressure swing adsorption (PSA)
are found to be more e$cient means of prepurifying
air. These methods employ beds of microporous adsor-
bent materials such as c-Al O , silica gel, zeolite
 
molecular sieves, etc. The choice between PSA and TSA
processes depends upon the size of the plant, availability
of regeneration gas and waste heat, etc. Usually for plants
with small capacities, puri"cation by PSA is more econ-
omical.
These adsorbents used in PSA/TSA processes may be
con"gured either in the form of separate beds, a bed with
layers of the two sorbents, or that composed of a mixture
of the two adsorbents. Most air-prepuri"cation designs
prefer a layered bed con"guration composed of a com-
posite of a weakly adsorbing sorbent and a strongly
adsorbing sorbent in order to minimize blowdown losses
and keep temperature excursions during pressure swing
to a minimum. A survey of the vast patent literature
pertaining to this process reveals that the most common
adsorbents for H O and CO removal by PSA and TSA
 
are activated alumina (c-Al O ) and molecular sieve
 
zeolites such as 13X zeolite (also known as NaX) (e.g.,
Sircar & Kratz, 1981; Kumar, 1987; Jain, 1993). More
recently, NaY zeolite has been suggested as a substitute
to 13X zeolite due to lower blowdown losses during the
desorption step and easier regenerability (Leavitt, 1998;
Golden, Kalbassi, Taylor & Allam, 1998; Kumar et al.,
1999). Also the adsorptive capacity of activated Al O is
 
said to be improved by alkalizing it with a basic solution
such as that of K CO (Golden et al., 1998). The patents
 
to Leavitt (1998) and Golden et al. (1998) also discuss the
removal of C H impurity in addition to H O and CO
   
removal.
In addition to synthetic zeolites, there is a large re-
source of naturally occurring zeolites such as clinop-
tilolite, which also have been shown to have excellent
potential for gas separation and puri"cation (Ackley,
Giese & Yang, 1992). By performing ion exchange of
clinoptilolite, for example, Ackley and Yang (1991a,b)
have shown that the adsorption characteristics of natural
zeolites can be tailored to suit a particular gas separation
application. Bulow, Dao and Fitch (1996) have claimed
that natural clinoptilolite and its ion-exchanged deriva-
tives, Ca>-clinoptilolite in particular, are suitable
sorbents for a PSA/TSA process for CO removal as part

of the prepuri"cation process. Also recent adsorption
studies on clinoptilolite have shown that the potential for
clinoptilolite as a sorbent for removal of water vapor
(Czepirski & Czepirska, 1992; White & Bussey, 1997;
Kasture et al., 1998), CO (Huesca, Diaz & Armenta,

1999; Triebe & Tezel, 1995), and hydrocarbons (Arcoya,
Gonzalez, Llabre, Seoane, Seoane & Travieso, 1996;
Ackley & Yang, 1991a) is encouraging. Hence, it would
be interesting to study the capacity of natural as well as
di!erent ion-exchanged forms of clinoptilolite for the
removal of air impurities.
Although the measurement of adsorption isotherms in
the very low-pressure range is vital for the design of
puri"cation processes, experimental data in literature is
scarce barring a few exceptions (Rudisill, Hacskaylo
& Le Van, 1992; Karwacki, Tevault, Buettner, Mahle
& Buchanan, 1999a, Karwacki, Buchanan, Mahle,
Buettner & Wagner, 1999b). This is primarily so because
of the empirical di$culties involved in the low concentra-
tion adsorption measurements. In this work, the adsorp-
tion isotherms and kinetics of the common air impurities
such as water vapor, CO , CH , C H , C H on com-
     
mercial 13X zeolite and c-Al O sorbents have been
 
measured in a broad concentration range varying
from a few ppm up to 1 atm. It must be noted however
that the main hydrocarbon impurity is C H since
 
its solubility in liquid O is much lower compared to

the other light hydrocarbons. However, since the experi-
mental measurements of low-pressure C H iso-
 
therms pose certain di$culties, the merits of the sorbents
have been judged by inspection of their capacity to re-
move other hydrocarbons such as CH , C H , and
  
C H .
 
In addition, the adsorption isotherms for these impu-
rities on a natural clinoptilolite and its K>- and Ca>-
exchanged forms have been studied and compared
against those of the commercial sorbents. The type of
adsorption isotherm which best "ts the low-pressure data
for these microporous sorbents and the use of H O

adsorption isotherm for evaluating pore size distribution
of zeolites is demonstrated.
 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838 4829

2. Experimental section

The adsorbent materials used for isotherm measure-

ments were as follows: 13X zeolite (Linde, lot
945084060002), c-Al O (PSD 350, Alcoa Inc.), and
 
natural clinoptilolite (TSM-140D, Steelhead Specialty
Minerals Inc., WA). The clinoptilolite, mined from quar-
ries at Mud Hills, California, was supplied in an impure
form containing soluble salts, and insoluble minerals
such as quartz, feldspar, and glass. The sample
was ground to 80 mesh size and only the soluble impu-
rities were removed by washing twice thoroughly with
copious amounts of warm deionized water followed by
"ltration and drying in an oven at 1103C. Ion exchange of
clinoptilolite with K>-ion was performed using the
method suggested by Ackley and Yang (1991a), whereas Fig. 1. Adsorption isotherm of N on sorbents under study at 295 K.

the same Ca>-clinoptilolite sample as that prepared in
an earlier work (Ackley & Yang, 1991a,b) was utilized in
the present study. It must be noted that although the K>-
clinoptilolite was nearly 100% exchanged, the Ca>-
clinoptilolite was only 89% exchanged.
The gases used in the analyses were supplied by
Matheson Gas Products, NJ, and their respective purities
and grades were as follows: N (99.998%, prepuri"ed),

O (99.6%, extra dry), CO (99.8%, bone dry), CH
  
(99%, CP grade), C H (99.5%, CP grade), and C H
   
(99%, CP grade). Water vapor isotherms were measured
by preparing a custom-built water vapor source for the
Micromeritics instrument. This source consisted of
a stainless-steel vessel (150 cm) containing 50 cm of
deionized water which was previously degassed by
boiling for 10 min to remove dissolved gases. The water
was further degassed by pulling a vacuum of 0.1 Torr
overnight. All the samples were ground to powder form
(80 mesh) and activated by heating the samples to 3503C Fig. 2. Adsorption isotherm of N on sorbents under study at 343 K.

in vacuo (10\ Torr) for 24 h to dehydrate and desorb
any adsorbed gases prior to each experiment. The iso-
therms were measured using a Micromeritics ASAP 2010
instrument, which is a static volumetric type of appar- sites and will also result in higher blowdown or vent
atus, and a Cahn TG-121 thermogravimetric analyzer losses during the desorption step of pressure swing ad-
(TGA). Isotherms were usually measured at two temper- sorption. Hence it is critical to study N adsorption

atures (295 and 343 K) for the purpose of determining characteristics of the candidate sorbents.
isosteric heats of adsorption. The N isotherms measured at 295 and 343 K for

the pressure range of 0}1 atm for the di!erent sorbents
are shown in Figs. 1 and 2, respectively. The capacities
3. Results and discussion of the sorbents for N were as follows: natural

clinoptilolite'K>-clinoptilolite'13X zeolite'Ca>-
3.1. Nitrogen clinoptilolite ' c-Al O . Since a high loading of N will
  
reduce the capacity of the sorbent for the impurities to be
Nitrogen (N ) is the most abundant component of air, removed (e.g., CO , H O, etc.) and also increase the vent
  
composing about 78% of the bulk. An ideal adsorbent loss under PSA operation, Ca>- clinoptilolite and c-
for air prepuri"cation should have a good a$nity for the Al O seem to be attractive candidates as sorbents due
 
impurities but at the same time it should also have to their low preference for N . The O isotherms
 
a negligible a$nity for gases such as N and O . This is which were measured at 295 K for the above sorbents
 
because a high loading of N on the sorbent will result in also showed a similar trend but are not included in this

increased competition to the impurities for adsorption work.
4830 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
Fig. 3. Adsorption isotherm of CO on sorbents under study at 295 K.
 
Fig. 4. Adsorption isotherm of CO on sorbents under study at 343 K.

3.2. Carbon dioxide
Carbon dioxide (CO ) occurs to the extent of

300}400 ppm in atmospheric air. The typical require-
ment for CO levels in prepuri"ed air is below 1.0 ppm.

Figs. 3 and 4 show the isotherms of CO on various

sorbents at 295 and 343 K, respectively. It is obvious
from the "gure that the best sorbent for CO removal,

especially at low partial pressures, is 13X zeolite while
c-Al O had the lowest capacity among the sorbents
 
considered. The CO adsorption capacities were ordered

as follows 13X'K>-clinoptilolite'natural clinop-
tilolite'Ca>-clinoptilolite'c-Al O . This observa-
 
tion is consistent with the fact that industrial processes
frequently use zeolites such as 13X to remove CO impu-

rity during air prepuri"cation as opposed to c-Al O as
 
is apparent from the patent literature. The high capacity
and the steep nature of the CO isotherm on 13X zeolite

make it the more suitable adsorbent to be used in a TSA
Fig. 5. Adsorption isotherm of H O on sorbents under study at 295 K.
process. The lower slope of the isotherm on c-Al O
 
leads to its use in a PSA process due to the greater
regenerability by pressure swing. It must be noted that
although Ca>-clinoptilolite has lower CO adsorption

capacities in the high pressure range, it has good adsorp-
tion characteristics in the low pressure range, which
would make it an ideal candidate for scavenging traces of
CO at the product end of the PSA bed. This result is in

good agreement with that observed by Bulow et al.
(1996).
3.3. Water vapor
Water vapor content in atmospheric air may vary from
0.1 and 3% v/v depending upon the geographic location.
The speci"cation of water vapor content in ASU feed air
is such that the corresponding dew point is lower than
the cryogenic temperatures used in N /O distillation.
 
Typically, the post-puri"cation prescribed maximum
water vapor content is 0.1 ppm. The adsorption iso-
therms of water vapor at 295 K on the sorbents under
study are shown in Fig. 5. It was observed that at higher
partial pressures (above 10\ atm or 100 ppm), 13X
zeolite had far superior adsorption capacity compared
to the other sorbents. For this range of H O con-

centration, the order of capacities is 13X' Ca>-clinop-
tilolite'K>-clinoptilolite+natural clinoptilolite'c-
Al O . However, in the low-pressure range (below
 
100 ppm), the order of capacities was slightly di!er-
ent: K>-clinoptilolite'c-Al O +natural clinoptilolite
 
'13X+Ca>-clinoptilolite. At extremely low concen-
trations ((10 ppm), Ca>-clinoptilolite showed good
promise as a sorbent. This behavior is similar to that
observed for CO , which further enhances the pros-

pects of using Ca>-clinoptilolite as a sorbent
towards the tail-end of the PSA bed for removing traces
of impurities.
 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
Fig. 6. Adsorption isotherm of CH on sorbents under study at 295 K.
  
Fig. 7. Adsorption isotherm of CH on sorbents under study at 343 K.

3.4. Hydrocarbons
Apart from removal of CO and H O, the air-pre-
 
puri"cation unit is also expected to remove traces of
hydrocarbons existing in the feed air. These hydrocar-
bons occur at ppm and sub-ppm levels in the atmosphere
and their concentration needs to be reduced to ppb
levels. Thus, ideally, their adsorption isotherms need be
studied at sub-ppm concentrations. However, the equip-
ment available for performing experiments were either
incapable or inaccurate for measuring isotherms at such
low partial pressures, especially due to very low loading
on the sorbents. Hence, the isotherms were studied
at higher concentrations (above 100 ppm) and the
merit of the sorbent for hydrocarbon removal was deter-
mined by a qualitative analysis of data in the higher
partial pressure range and by extrapolation to low con-
centrations.
The isotherms of CH at 293 and 343 K are shown in

Figs. 6 and 7 respectively. The following was the order of
4831
Fig. 8. Adsorption isotherm of C H on sorbents under study at
295 K.
Fig. 9. Adsorption isotherm of C H on sorbents under study at
 
343 K.
preference for CH : K>-clinoptilolite '13X'natural

clinoptilolite+Ca>-clinoptilolite'c-Al O . Figs. 8
 
and 9 show the corresponding isotherms for C H at two
 
temperatures, whereas Figs. 10 and 11 show the capaci-
ties for the same on C H . The order of a$nity of the
 
sorbents for the C hydrocarbons remained more or less

similar to that for CH . This result is also entirely consis-

tent with the fact that zeolites such as 13X are used
conventionally for hydrocarbon removal in industrial
units. It must be noted though that the most important
hydrocarbon impurity in air is C H . Although it occurs
 
at a trace level in the atmosphere, it can accumulate in
the reboiler section of a distillation column over time and
pose an explosion hazard. The adsorptive capacity of the
sorbents for C H was not measured in this work, but
 
the order of a$nity is expected to be similar to that
observed for the other hydrocarbons.
4832 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838

The kinetics of adsorption of the N as well as most of

the impurities mentioned above was found to be fast, i.e.,
adsorption was found to be complete within 10 s. The
adsorption of hydrocarbons such as CH in clinoptilolite

however was found to be relatively slower (Ackley
& Yang, 1991a) taking about 200 s for completion. This
Fig. 10. Adsorption isotherm of C H on sorbents under study at
 
295 K.
might result in a longer mass transfer zone in the PSA
bed for the hydrocarbons.
3.5. Heats of adsorption
The adsorption isotherms of the various impurities on
the sorbents considered at two temperatures were em-
ployed for evaluating the adsorption enthalpy. For this
purpose, the Clausius}Clapeyron equation was applied
to the isotherm data at the two temperatures for the
purpose of calculating the isosteric heats of adsorption
(*H ). The tabular data for the *H values for the
 
corresponding adsorbates is summarized in Table 1. It
was observed that the heat of adsorption showed a con-
siderable dependence on surface coverage in some cases
due to surface energetic heterogeneity. The values in
Table 1 are average values obtained at average surface
loadings in the range of typical PSA operation. On in-
spection of the table, it is apparent that 13X zeolite has
the highest *H values while c-Al O had the least for
  
almost all the sorbates considered. During the PSA cycle,
the component that is adsorbed and desorbed to the
highest extent is N , however depending upon feed con-

ditions, the adsorbed amounts of other components may
also be important. A study of *H is signi"cant since

a high heat of adsorption can result in large temperature
excursions during adsorption and desorption steps of
the PSA cycle, which can drastically a!ect the perfor-
mance of the puri"cation process. From this point of
view, c-Al O is an ideal sorbent which would minimize
 
heat e!ects during the PSA operation.

3.6. Adsorption Isotherm

The experimental adsorption isotherm data collected

in this work needed to be "t to an isotherm model to
extend its utility. The conventional isotherm models
used in literature are the Langmuir equation, Lan-
gmuir}Freundlich (also known as loading ratio correla-
tion: LRC), and the Tòth isotherm (Valenzuela & Myers,
1989). These models are popular in PSA simulation liter-
Fig. 11. Adsorption isotherm of C H on sorbents under study at
 
ature due to their simplicity and their non-iterative
343 K. nature, and are summarized below:

Table 1
Heats of adsorption

*H (kcal/mol)

N CO H O CH C H C H
       
13X 4.0 8.2 12.3 3.3 8.4 7.5
c-Al O 2.0 8.0 11.6 2.5 7.0 4.2
 
Nat. clinoptilolite 5.5 10.1 14.4 2.0 6.0 6.5
K>-clinoptilolite 6.0 9.5 * 6.0 6.4 7.0
Ca>-clinoptilolite 4.8 6.0 * 3.6 5.2 2.5
 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
Langmuir model:
q bP
q" K . (1)
1#bP
Langmuir}Freundlich (LRC) model:
q bPL
q" K . (2)
1#bPL
To% th model:
aP
q" . (3)
(d#PI)I
For bulk separation involving high concentration of
gases, the above models are adequate for "tting the
isotherm data. However, the same may not hold true for
puri"cation problems which involve adsorption at very
low concentrations. Indeed, most studies dealing with
low concentration adsorption seem to favor the
Dubinin}Radushkevich (DR) model to describe the iso-
therm (e.g., Karwacki et al., 1999a,b). Another recom-
mended model is the modi"ed Antoine equation of
Hacskaylo and LeVan (1985). This model is based on the
well-known Antoine's equation for calculation of vapor
pressures, but has surface loading dependent Antoine's
constants. The model was found to be successful over
a wide range concentration range from trace values to
saturation for activated carbon adsorbent, and had lower
variances compared to both the DR equation, as well as
the DA (Dubinin}Astakhov) equation. However the
main disadvantage of this model is the implicit form of
the equation which gives P"P(h, ¹), instead of the more
traditional form: h"h(P, ¹). Also such a equation would
be di$cult to extend to multicomponent gas mixtures,
unlike the other models.
The step-like nature of isotherms (for rectangular co-
ordinate plots) at low pressure for microporous sorbents
may be explained by their narrow pore size distributions.
The adsorption isotherms fall drastically below a certain
threshold partial pressure, primarily because the free
energy change required to adsorb a molecule at a very
low partial pressure is very large. An extremely small-
sized pore is required so that the magnitude of its energy
potential is large enough to provide the required free
energy change (Horvàth & Kawazoe, 1983). Most micro-
porous materials have a steeply falling pore size distribu-
tion in the micropore range, and consequently
adsorption below the threshold partial pressure also falls
steeply. A study of the low-pressure isotherm data for the
various air impurities shown in Figs. 3}11 does re#ect
this fact. The isotherm data seems to fall rapidly in the
very low-pressure range in most cases. Such a trend
cannot be predicted well by models such as the Lan-
gmuir}Freundlich (LRC), Tòth, etc., as will be shown
shortly.
On the other hand, potential theory based approaches
such as the Dubinin}Astakhov (DA) (a generalized ver-
4833
sion of the Dubinin}Rudushkevich model) equation is
better suited to "t concentration isotherm data for micro-
porous sorbents at low pressure. This equation has three
"tting parameters (< , bE, and m) and is usually given in

the following form (Yang, 1997):
Dubinin}Astakhov (DA) model:


R¹ P K
<"< ) exp ! ln Q . (4)
 bE P
The exponent m represents the distribution of the adsorp-
tion energies of the adsorbent. Large m values are found
for sorbents with a narrow distribution of micropores,
whereas small m values represent sorbents with wide
ranges of pore sizes. The volume of the adsorbed sorbate
(<) as well as the limiting micropore volume of the
adsorbent material (< ) can be converted into molar

adsorbed amount (n) and limiting molar adsorbed
amount (n ), respectively by dividing both sides of Eq. (4)

by the molar volume of the sorbate (< ). Various
K
methods to calculate < have been discussed by Doong
K
and Yang (1988). The saturation pressure (P ) can be
Q
found using the reduced Kircho! equation at temper-
atures above the normal boiling point (Yang, 1997).
Thus, Eq. (4) above can now be more conveniently writ-
ten as


P K
n "n exp ! C ln Q , (5)
  P
where
R¹
C"
bE
. (6)
The parameters n and C are temperature dependent,

whereas for small temperature variations, the exponent
m and saturation pressure P may be assumed to be
Q
essentially invariant with temperature.
Fig. 12 shows the isotherm data of H O on 13X zeolite

at 295 K and that of CO at 295 and 343 K along with

the LRC, Tòth, and DA "ts for the same. It can be seen
from the "gure that there is a large deviation of the LRC
model trends from the isotherm data particularly at low
partial pressures. The Tòth isotherm "t is marginally
better than the LRC model; however, the DA equation
seems to "t the data the best over the entire range of
concentration. This justi"es the use of the DA equation
in the modeling of the air-prepuri"cation PSA process.
The e!ectiveness of the DA equation is exhibited again in
Fig. 13, which shows a similar plot of H O and CO
 
isotherms on c-Al O . The various parameters of the
 
LRC, Tòth, and the DA equation (Eqs. (2), (3) and (5))
which were "t to the pure component adsorption data of
certain gas-adsorbent systems are given in Table 2. It
should be noted that for simplicity, the P values used in
Q
the DA isotherm "ts for the two-temperature data, have
been kept independent of temperature.
4834 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838

The success of the DA equation over the others in

"tting the low concentration data can be explained by the
adsorption energy distribution of the sorbent for the
various models as explained in detail in the book by

Fig. 14. Energy distribution function F(E) of 13X zeolite adsorbent as

determined from the "ts of Langmuir}Freundlich, Tòth, and
Dubinin}Astakhov models.
Fig. 12. Langmuir}Freundlich, Tòth, and Dubinin}Astakhov model
"ts to adsorption isotherm data of H O (295 K), and CO (295 K,
 
343 K) on 13X zeolite. Jaroniec and Madey (1988). For the Langmuir}Freun-
dlich equation (LRC), and the Tòth equation, the energy
distribution function F(E) is determined by the exponents
in Eqs. (2) and (3), namely n (LRC), and k (Tòth) which
are also known as heterogeneity parameters. The F(E) for
the DA equation, on the other hand, is determined by
two parameters: the a$nity coe$cient C, and the hetero-
geneity parameter m. Hence, there is a greater #exibility
in "tting the sorbent energy distribution pro"le using the
DA equation.
The energy distribution for the isotherm "ts of the
various models discussed above for CO on 13X zeolite

at 343 K were plotted using the equations given by
Jaroniec and Madey (1988) and are shown in Fig. 14. The
mean energy for the pro"les was assumed to be equal to
the mean heat of adsorption of CO on 13X zeolite. The

Langmuir}Freundlich (LRC) equation is seen to possess
Fig. 13. Langmuir}Freundlich, Tòth, and Dubinin}Astakhov model a symmetrical quasi-Gaussian energy distribution func-
"ts to adsorption isotherm data of H O (295 K), and CO (295 K,
 
tion F(E). The Tòth isotherm also seems to have a quasi-
343 K) on c-Al O . Gaussian distribution, but in this case, F(E) is skewed
 

Table 2
Values of the Langmuir}Freundlich (LRC), Tòth, and the Dubinin}Astakhov (DA) model parameters "t to experimental isotherm data

LRC Tòth DA
q (mmol/g) B (atm\L) n A (mmol/g) D (atmI) k n (mmol/g) C m
K 
H O/13 X 293 K 20.93 18.93 0.43 28.09 0.05 0.24 16.0 0.125 6.0

CO /13 X 293 K 5.24 19.43 0.70 13.00 0.18 0.30 7.05 0.120 3.0

CO /13 X 343 K 4.81 5.23 0.70 12.84 0.31 0.30 4.32 0.136 3.0

H O/c-Al O 293 K 5.06 9.29 0.40 14.86 0.12 0.20 2.81 0.107 6.0
  
CO /c-Al O 293K 1.11 3.64 0.70 3.49 0.43 0.30 0.74 0.147 2.5
  
CO /c-Al O 343 K 0.27 6.46 0.70 2.06 0.59 0.30 0.65 0.187 2.5
  
Values of P used were as follows: (1) P (CO )"57.53 atm, (2) P (H O)"1.0 atm, at all temperatures.
Q Q  Q 
 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
and there is broadening of the energy distribution in the
direction of low adsorption energies. As a result the Tòth
isotherm predicts more weak adsorption sites than the
other models. Since the weak adsorption sites are bound
to be occupied at higher pressures, the Tòth isotherm is
apt for describing systems with steeply rising isotherms in
the high-pressure range. The DA equation on the other
hand has been shown to have a quasi-Gaussian distribu-
tion with a broadening at high adsorption energies, al-
though this broadening decreases as the parameter m
increases. In reality, the latter form of energy distribution
seems to be a characteristic of many real adsorbent
surfaces and for adsorption at low pressures, it is the
high-energy sites which are signi"cant. Hence, the DA
equation has a greater utility in describing low-pressure
adsorption isotherms. The extrapolation of the DA iso-
therm to yet lower pressures should however be carried
out with caution. It is a well-known drawback of the DA
equation that it does not tend to Henry's law as pressure
tends to zero. It is believed that the DA equation holds
only till a certain characteristic relative pressure below
which the Henry's law becomes the more appropriate
model (Jaroniec & Madey, 1988). Ways to correct the
drawback the DR equation by splicing a Henry's law
equation have been discussed in literature (Kapoor,
Ritter & Yang, 1989).
3.7. Pore size distribution
The determination of the pore size distribution (PSD)
is an important aspect of characterizing microporous
sorbents. Various techniques exist for evaluating PSD of
a microporous material such as the measurement of
saturated amounts of probe molecules of various sizes,
and by measurement of a single adsorption isotherm of
gases (or vapors) at subcritical temperatures. In the latter
event, statistical mechanic tools such as density func-
tional theory (DFT) or alternatively, potential-theory
based methods like Horvàth}Kawazoe (HK) equation
can be used. The Horvàth}Kawazoe method (Horvàth
& Kawazoe, 1983) is a preferred technique due to its
computational simplicity. Traditionally, adsorbates such
as N (77 K) or Ar (87 K) are used for determining the

PSD of a material, although in recent times the possibili-
ty of using other sorbates such as CO (Horvàth et al.,

1998) and CH Cl (Mariwala & Foley, 1994) are being

explored.
The HK equation to be used depends upon the type of
pore geometry of the sorbent. For materials character-
ized by continuous channel like pores such as clinop-
tilolite, the cylindrical pore geometry HK model derived
by Saito and Foley (1991) is the most suitable. Certain
materials such as 13X (NaX) zeolite, however, are charac-
terized by pores resembling spherical cavities. In such
cases the HK equation for spherical pore geometry given
by Cheng and Yang (1994) needs to be used. Cheng and
4835
Yang (1994) also introduced a correction factor to ac-
count for the non-linearity of the isotherm at higher
pressures which has a sharpening e!ect on the pore-size
distribution.
Attempts at determining the PSD of sorbents like
activated carbon using water vapor isotherms have been
made in the past by using empirical relations relating the
area of the adsorption}desorption hysteresis loop to pore
width (Tsunoda, 1991; Tamai, Nishida & Suzawa, 1991;
Russell & LeVan, 1994). In this work, the possibility of
evaluating the pore size distribution of zeolite samples
using water vapor isotherms using the HK model was
explored. The advantage of using water vapor as a probe
molecule is that it is readily available and the analysis can
be carried out under ambient conditions. However, the
HK model is based on simple van der Waals interactions,
and the electrostatic forces between the sorbate and
sorbent are neglected. In the case of water}zeolite system,
the polar water molecule has strong electrostatic interac-
tions with the oxide ions of the zeolite framework as well
as the metal ions present in the zeolite framework. Hence,
there is a need to adjust the parameters of the HK model.
All adsorbate parameters and all except one adsorbent
parameter in the present study were obtained from litera-
ture sources. The PSD of the adsorbents are known from
crystallographic studies reported in literature. The sur-
face density of the oxide ions on the adsorbent surface
(N ) was "t to obtain the PSD of the samples in the
Q
required range.
The PSD of three sorbents was evaluated using the
H O isotherm by the HK method, namely 13X zeolite,

K>-clinoptilolite, and Ca>-clinoptilolite. Fig. 15 shows
the PSD of 13X zeolite using the HK spherical-pore
geometry equation with and without the Cheng-Yang
correction. The known crystallographic diameter of 13X
Fig. 15. Pore size distribution (PSD) of 13X zeolite determined from
H O adsorption isotherm at 295 K using the Cheng}Yang spherical

pore version of the Horvath}Kawazoe equation. The solid line shows
the PSD with Cheng}Yang correction and the dotted line shows the
same without the correction.
4836 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838

Table 3
Values of the parameters used in the determination of pore size distri-
bution of sorbents using the Horvàth}Kawazoe equation

Adsorbate properties (H O)

s Magnetic susceptibility 2.15;10\ cm

a Polarizability 1.45;10\ cm

D Kinetic diameter 2.65 As


N No. of sorbate m'cles/unit area 7.35;10 molecules/cm

Adsorbent properties (zeolite)
s Magnetic susceptibility 1.30;10\ cm
1
a Polarizability 2.50;10\ cm
1
D Kinetic diameter 2.76 As 
1
N No. of O- ions/unit area:
1
13X Zeolite 1.72;10 molecules/cm
K>-clinoptilolite 4.37;10 molecules/cm
Ca>-clinoptilolite 8.46;10 molecules/cm

Weast (1989). Fig. 16. Pore size distribution of K>-clinoptilolite determined from

Breck (1974). H O adsorption isotherm at 295 K using the Saito}Foley cylindrical

Estimated from liquid density. pore version of the Horvath}Kawazoe equation. The solid line shows
Cheng and Yang (1994). the PSD with Cheng}Yang correction and the dotted line shows the
Estimated in this work. same without the correction.

zeolite is 13.7 As . The values of the HK parameters used

for the calculations are summarized in Table 3. The value
of the surface density of molecules N corresponding to
Q
this PSD, was 1.72;10 molecules/cm, was almost
double the accepted value for a faujasite cavity, namely
8.48;10 molecules/cm (Barrer, 1978). The require-
ment for a higher N value is due to the additional
Q
electrostatic interactions which are unaccounted for in
the HK model. The PSD for K>-clinoptilolite is shown
in Fig. 16. The structure of clinoptilolite consists of inter-
crossing channels made up of 8- and 10-member rings
that are non-planar (Ackley & Yang, 1991b). Since the
cylindrical pore structure comes closest to the clinop-
tilolite channel structure, the HK cylindrical-pore model
was used. The majority of the channels have a dimension
of 7.2;4.4 As which agrees with the PSD shown in Fig. 17. Pore size distribution of Ca>-clinoptilolite determined from
Fig. 16. Similarly, Fig. 17 shows the PSD of Ca>-clinop- H O adsorption isotherm at 295 K using the Saito}Foley cylindrical

tilolite giving the pore size of the same order. Here the pore version of the Horvath}Kawazoe equation. The solid line shows
Cheng}Yang correction yielded a signi"cantly better re- the PSD with Cheng}Yang correction and the dotted line shows the
same without the correction.
sult due to the curvature of the isotherm. The corre-
sponding "t value of N for the Ca>-clinoptilolite
Q
(8.46;10 molecules/cm) was about 20% that for K>- low pressure water vapor isotherms may limit the scope
clinoptilolite (4.37;10 molecules/cm). This shows of its application.
that the electrostatic interaction of H O with K>-ions

was about "ve times as strong as that with Ca>-ions.
One of the factors for the stronger interaction with K>- 4. Conclusions
ions is that stoichiometrically there are twice the number
of univalent K>-ions as there are divalent Ca>-ions in The adsorption characteristics of typical impurities in
the sorbent framework. The good agreement of the HK air fed to the air-separation cryogenic distillation, i.e.,
predicted PSD and crystallographic data lends credence CO , H O and hydrocarbons such as CH , C H , and
    
to the experimentally measured water vapor isotherms. It C H were studied on adsorbents such as 13X zeolite,
 
also demonstrates that despite the strong polarity of the c-Al O , natural clinoptilolite, K>-clinoptilolite and
 
water molecule, water may serve as a probe molecule for Ca>-clinoptilolite in the medium to low pressure range.
PSD estimation. However, the di$culties in obtaining The adsorption kinetics of most of the components was
 S. U. Rege et al. / Chemical Engineering Science 55 (2000) 4827}4838
found to be fast enough to assume instantaneous equilib-
rium. A study of the adsorption isotherms revealed that
13X zeolite and K>-clinoptilolite were ideal sorbents
for CO removal whereas c-Al O had the least capacity
  
for the same. For removal of moisture content from
the feed stream, K>-clinoptilolite and c-Al O
 
were found to be ideal in the 100 ppm and lower concen-
tration range. The C and C hydrocarbons seemed to
 
have the highest a$nity to K>-clinoptilolite and 13X
zeolite and the least a$nity to c-Al O . An ideal sorbent
 
for air-prepuri"cation should also have a low capacity
for the major components of air, namely N and O .
 
Sorbents such as c-Al O and Ca>-clinoptilolite were
 
found to be most suitable in this respect. These observa-
tions will enable a preliminary screening of sorbents for
the air-prepuri"cation process using pressure swing
adsorption.
Isotherm models such as the Langmuir}Freundlich
(or loading ratio correlation), Tòth, and the Dubinin}
Astakhov (DA) equation were used to "t the isotherm
data. It was found that the DA equation gave the best "t
to the data in the low-pressure range since its mathemat-
ical form had the best #exibility to "t the energetic
heterogeneity of the sorbent. Also since the derivation of
the DA model is on the basis of the energy potential
rather than adsorption kinetics, it is expected to describe
adsorption in micropores to a better degree than conven-
tional models such as Langmuir}Freundlich and Tòth.
Finally, the use of H O adsorption isotherms were
 We are grateful to Stefan Zajic, visiting student from
used for the evaluation of the pore size distribution of
13X zeolite, K>-clinoptilolite, and Ca>-clinoptilolite
was demonstrated. It was found that since electrostatic
interactions were not incorporated in the HK model, the
surface density of oxide ions (N ) on the adsorbent sur-
Q
face needed to be adjusted. The "t values, though di!er-
ent from the value reported in previous literature for
zeolites, were within a physically realistic range. Despite
the polarity of H O molecules, it may serve as a good

probe molecule for PSD estimation provided the di$cul-
ties of obtaining low pressure H O isotherms are over-
 Untapped potential for kinetic gas separations. Zeolites, 12(7),
come.
Notation
a Tòth parameter, mmol/g
b Langmuir}Freundlich parameter, atm\L
C DA equation parameter, dimensionless
d Tòth parameter, atmI
D kinetic diameter of molecule, As
F(E) energy distribution function of adsorbent sur-
face, mol/kJ
*H heat of adsorption, kcal/mol

k Tòth parameter, dimensionless
m DA equation parameter, dimensionless
n Langmuir}Freundlich parameter, dimensionless
n adsorbed amount, mmol/g

4837
n limiting micropore adsorbed amount, mmol/g

N Avogadro's number, molecules/mol

N surface density of molecules, molecules/cm
P partial pressure, atm
P saturation pressure, atm
Q
q adsorbed amount, mmol/g
q Langmuir}Freundlich parameter, mmol/g
K
R gas constant, J/mol/K
¹ absolute temperature, K
< volume adsorbed in micropores, cm/g
< molar volume of adsorbate, cm/mol
K
< limiting micropore volume, cm/g

Greek letters
a polarizability, cm
b DA equation parameter, dimensionless
s magnetic susceptibility, cm
h Surface coverage, dimensionless
Subscripts
A adsorbate
S adsorbent
Acknowledgements
University of Pennsylvania, for measuring part of the
adsorption isotherms and calculating heats of adsorp-
tion. The work was supported by NSF under CTS-
9819008.
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