Adsorption of Water Vapour on Activated Alumina.

I -
Equilibrium Behaviour
R. DESAI, M . HUSSAIN and D. M . RUTHVEN

Department of Chemical Engineering, University of New Brunswick, P. 0. Box 4400, Fredericton, NB E3B SA3

Equilbrium isotherms are reported for adsorption of water vapour on several different activated alumina adsorbents.
The experimentally measured isotherms represent the sum of the contributions from water vapour held in several ways
but these contributions can be resolved by detailed analysis. The individual isotherms conform closely to simple ideal-
ized models (Langmuir for chemisorption, BET for physisorption), thus providing a rational basis on which to compare
different samples and the effects of different regeneration procedures. The apparent complexity in the behaviour of
these systems arises from the superposition of the different contributions, the relative importance of which depends
upon the nature of the sample and the regeneration conditions. By contrast, the behaviour of the resolved isotherms
is relatively straightforward.

On prCsente des isothermes dCquilibre pour ladsorption de la vapeur deau sur differents adsorbants dalumine activee.
Les isothermes mesurCs expCrimentalement reprksentent la somme des contributions de la vapeur deau retenue de
diffkrentes faCons, mais ces contributions peuvent Stre rksolues par une analyse dCtaillCe. Ces diffkrents isothermes
se conforment Ctroitement aux modtles idtalisks simples (Langmuir pour la chimisorption, le BET pour la physisorp-
tion), fournissant ainsi une base rationnelle I? partir de laquelle on peut comparer les differents Cchantillons ainsi que
les effets des mCthodes de r6gCnQation. La complexit6 apparente du comportement de ces systltmes rCsulte de la super-
position de ces diff6ren:es contributions, dont limportance relative depend de la nature de ICchantillon et des condi-
tions de rCgCnCration. A Iinverse, le comportement des isothermes rksolus est relativement simple.

Keywords: alumina, water vapour, capillary condensation, physisorption, chemisorption.

T he activated aluminas used in adsorption and catalysis

are generally high surface area microporous forms of
aluminum oxide produced by thermal dehydration of alu-
minum hydroxides or hydrated aluminas (A1203 * 3H20 and
A1203 . H20). The low temperature form of activated alu-
mina known as y-alumina, which in fact consists of a mix-
ture of different microcrystalline forms ( p , x, y , and q), is
produced at dehydration temperatures up to 600C. There
is, however, some ambiguity in this terminology since the
term y-alumina is also sometimes applied to a single crys-
talline phase. In this paper we use the term y-group to refer
to the mixed phase while the term y-alumina is reserved
for the crystalline form. The chemical activity and active
adsorption sites result from the defect structure produced
during the amorphous to crystalline transition which occurs
during the thermal dehydration process. Since the activated
materials generally fall somewhere between the amorphous
and crystaline forms they are sometimes referred to as tran-
sition aluminas. The interaction between water and an alu-
mina surface is complex and involves several different types
of surface forces. Although extensive and detailed studies
of the H20-alumina system have been reported in connec-
tion with research into the catalytic properties of alumina,
the results of these investigations have not been fully
integrated into the studies of alumina as a desiccant.
This paper presents the results of an experimental program
which was carried out to determine the equilibrium adsorp-
tion charactristics of a number of commercial alumina
samples. Complete adsorption and desorption isotherms have
To whom correspondence may be addressed.
been measured and the hysteresis loops for both chemisorp-
tion and capillary condensation are clearly identified. It was
quickly realised that a dry alumina sample retains water
vapour in several different ways, including both reversible
and irreversible adsorption. The nature of these forms can
be identified by reference to the fundamental studies alluded
to above. As a result, an experimental equilibrium isotherm
is in fact the sum of several different contributions. To obtain
a clear understanding of equilibrium data it is necessary to
separate these contributions. By decoupling the composite
isotherms complete physisorption and chemisorption
isotherms have been determined. The equilibrium measure-
ments were carried out by gravimetric and dynamic tech-
niques and the data obtained by both techniques are quite
consistent.
Interaction between water and an alumina surface
Most but not all transition aluminas have the defect spinel
structure. The details of the spinel structure are given by
Clark (1971). The complexity of the surface chemistry of
the activated aluminas arises because the proportions of the
various transition aluminas and their defect structures are
sensitive to the conditions under which the material is
dehydrated. The alumina surface is amphoteric, containing
both acidic and basic sites of varying strengths and concen-
trations. Acidity results from the presence of coordinately
unsaturated A l f 3 ions and acidic hydroxyls while basic
sites arise from the presence of 0-2 anions and basic
hydroxyls. Among the earliest detailed studies of the sur-
face are those of Peri (1965a, 1965b) and Peri and Hannan

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, AUGUST, 1992 699
 TABLE1
Samples of Activated Alumina Studied
Sample Manufacturer
PSA-I Alcan
PSA-I1 Alcan
AA 100 Alcan
AA200X Alcan
ID 880105 Alcan
AA 300 Alcan
RP A-grade Rhone-Poulenc
H-152 Alcoa
LDS 350 Alcoa
(1960) who developed a model for the progressive dehydrox-
ylation of a a-alumina surface which could account for the
presence of the five different types of acidic and basic
hydroxyl groups observed by infra-red spectroscopy. This
model has been refined by Knozinger and Ratnasamy (1978).
Studies of water vapour equilibrium have been reported
by Cornelius et al. (1955), De Boer et al. (1963), De Boer
and Lippens (1964), Lippens et al. (1964), Lippens and
Deboer (1964), Carruthers et al. (1971), Morimoto et al.
(1969, 1971) and Bailey and Wightman (1979). In all these
studies the major objective was to relate the catalytic proper-
ties to the surface characteristics. In the light of these and
other studies it is evident that the water vapour held on an
alumina surface may be present in chemisorbed form, in
physisorbed form or as capillary condensate within the pores.
Chemisorbed water is really the surface hydroxyls and the
properties of these groups are determined by their coordi-
nation number and net electrical charge.
A monolayer of hydrogen bonded water molecules covers
the surface hydroxyls such that the H20:OH ratio is 1:2 and
this hydrogen bonded water is sometimes described as quasi
chemisorbed. An additional layer of water molecules may
be physically absorbed on top of the hydrogen bonded layer
and, depending on the pore size and relative pressure, they
may also be capillary condensation within the smaller (meso
and macro) pores. Although sufficient experimental evidence
is available to support these distinctions between differently
held forms of water our understanding of the nature of the
surface structure is based on somewhat idealized models.
The adsorptive properties of activated alumina were first
recognized by Folkers and Shovel (1901). Since then a
number of studies of the equilibrium characteristics of H20-
alumina system have been reported in the literature. Due to
the complex nature of the H20-alumina interaction, the
equilbrium characteristis are still not fully understood. In
most investigations (Jury and Horng, 1973; Goodboy and
Fleming, 1984; Fleming, 1986; Munro and Johnson, 1925,
1926) only adsorption isotherms are reported and these are
generally found to be not fully reversible. Bailey and
Wightman (1979) have reported hysteresis, but there appears
to have been no attempt at a detailed study of this
phenomenon, which is practically important in the evalua-
tion of the economics of regeneration of alumina gel driers.
Also the Type I1 isotherm (Type I1 refers to Brunauers clas-
sification. See Ruthven, 1984) for water vapour on alumina
may have a significant effect on the nature of the concentra-
tion front and breakthrough time in commercial applications
when a relatively high water vapour level is present in the
process stream.
700 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70. AUGUST. 1992
Details of sample
Prepared by reverse prcipitation, activated by
conventional method.
Prepared by reverse precipitation, and micro-
wave activated.
Prepared by conventional method, activated
by rapid dehydration.
Commercial sample.
Prepared and calcined by conventional method.
Commercial sample.
Commercial sample.
Commercial sample.
Commercial sample.
Experimental methods
Sorption isotherms for water vapour on various different
activated alumina adsorbents were determined by both gravi-
metric and dynamic methods. Commercial alumina samplcs
from Rhone-Poulenc, Alcan and Alcoa as well as some newly
developed samples from Alcan research laboratories were
used (see Table 1). The isotherms measured by different tech-
niques were good in agreement and this is further discussed
in a subsequent section.
Gravimetric measurements were carried out in a vacuum
micro electrobalance system (Cahn Instrument Co., Para-
mount, CA) fitted with Barocel capacitance manometers
(Datametrics Co., Watertown, MA) for pressure measure-
ment. Prior to the measurements the sample was regener-
ated by evacuation to lop3at 250 or 350C overnight. It
was found that when the sample was cooled to the adsorp-
tion temperature after overnight degassing (dehydration) it
picked up water from the glass walls of the vacuum system.
This clearly shows the exceptional affinity of dry activated
alumina for traces of water vapour. This characteristic of
activated alumina has an important bearing on the measure-
ment and correlation of capacities for water adsorption but
this has not been clearly addressed by most researchers. In
some cases the dry weight is not stated (Jury and Horng,
1973) and in other instances it is based on an arbitrarily
selected regeneration temperature (Bailey and Wightman,
1979). Although the total water vapour content of a sample,
degassed at room temperature, can be obtained at 1100 to
1200C, a procedure used by Peri (1965a,1965b), Peri and
Hannan (1960), De Boer et al. (1963), DeBoer and Lippens
(1964), Lippens and DeBoer (1964), Lippens et a1 (1964)
and Morimoto et al. (1969, 1971), the dry weight obtained
by this procedure cannot be used as a basis for expressing
the equilibrium isotherm because part of the water is irrever-
sibly associated with the activated alumina lattice. Cornelius
et al. (1955) used the dry weight at the regenation tempera-
ture (538C) to express the water vapour isother at 35C.
The choice in the present studies of a dry weight measured
at regeneration temperature (in most of the measurements
350C) is justified as follows.
A sample was completely equilbrated with water vapour
at 25C (the reference temperature). It was then degassed
for a period of 48 h at the same temperature to remove all
the physisorbed water. The temperature was then gradually
raised while evacuation was continued, to drive off the quasi-
chemisorbed water (water that it adsorbed on the surface
hydroxyls through hydrogen bonds). It was observed that for
most of the commercial samples the amount of water
 TABLE2
Surface Area of Activated Alumina Samples Under Different
Regeneration Conditions
Sample S,(m/g) Comment
Alcan AA200X 38 I Regenerated at 350C.
Alcan AA200X 295 Regenerated at 200C.
Alcan AA2OOX 244 Regenerated at 450C.
Alcan AA300 325 Regenerated at 350C.
Alcan AA300 323 Repeatedly regenerated at 350C.
Alcan PSA-I 38 I Regenerated at 350C.
Alcan PSA-I1 385 Regenerated at 350C.
Alcoa HI52 388 Regenerated at 350C.
Rhone-Poulenc 360 Regenerated at 350C.
corresponding to a monolayer of water molecules (as deter-
mined by nitrogen adsorption) was eliminated under high
vacuum over a 24 hour period. It is well known that porous
particles sinter at higher temperatures due to changes in the
pore structure which can reduce the specific area. However,
this is not a significant effect at 350C (Misra, 1986). From
BET area measurements it was found that, despite repeated
dehydration at 350C, the specific surface area of the sample
remained constant (Table 2 , sample-Alcan AA300). This
temperature was therefore chosen as the dehydration tem-
perature and the dry weight was also based on the same
temperature.
Some adsorption isotherms were also determined from
measurements of the breakthrough curves for water vapour
from a helium carrier in a small packed column. Equilibrium
capacities were calculated from a mass balance over the
column
(q0/c,)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
The stoichiometric time f and the equilibrium capacity qo
were determined by integrating the experimental break-
through curves (for further details refer to Ruthven, 1984).
Pore size distributions were measured (byoAlcan)by gas
adsorption, for pore diameters less than 100 A , and by mer-
cury penetration for pore diameters greater than 100 A . BET
areas were measured by the nitrogen adsorption at liquid
nitrogen temperature in a Perkin-Elmer Sorptometer.
Results and discussion
CRITERION FOR REGENERATION TEMPERATURE
In practical systems regeneration is generally carried out
with an inert purge or with a circulation loop containing a
condenser. The choice of regneration temperature plays an
important role in the application of alumina as a desiccant.
For economic reasons it is important in terms of thermal
energy requirements and service life. An adosrbent that
requires high temperature dehydration for prolonger periods
of time may eventually loose its sorption characteristics.
From the operational point of view the regeneration is gener-
ally carried out with an inert purge or with a recycle stream
with continuous condensation. Proper design requires data
on desorption isotherms but only very little work has been
reported in the literature on this aspect of the water-alumina
system.
The complex nature of water-alumina interaction in terms
of the various different contributions from chemisorbed,
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, AUGUST, 1992
-, , _-----I
+ , 3ia.L
Figure 1 - Effect of regeneration temperature o n adsorption ot
water vapour on activated alumina (Alcan AA200X) at 26C.
quasi-chemisorbed and physisorbed water makes it very
difficult to specify the optimal dehydration temperature in
a general way. Data on thermal dehydroxylation (surface
OH-density of alumina as a function of pretreatment tem-
perature) given by Knozinger and Ratnasamy (1978) are
applicable for all types of activated alumina. From this, one
can estimate the available chemisorption capacity at a par-
ticular dehydration temperature. Such information is useful
in catalytic applications in order to determine the number
of active sites on the surface. In adsorption, one cannot
strictly follow this procedure as the removal of surface
hydroxyls after a certain temperature (which depends on the
surroundings) can change the surface into a different form
of transition alumina. Therefore the properties of the regener-
ated alumina are not necessarily the same as the properties
of the original material. Thus it is clear that, for adsorptive
service, removal of the chemisorbed water may not be
desirable. The choice of dehydration temperature is there-
fore a matter of determining the temperature at which the
physisorbed and quasichemisorbed water are most effectively
removed from the bed.
In the present study a preliminary series of measurement
swas made to establish the effect of initial dehydration tem-
perature on sorption capacity (Figure 1). It is evident that
the dehydration at 350C gives higher capacity than dehydra-
tion at both 200 and 470C. These observations are readily
explained; at 200C dehydration is incomplete since the sur-
face area obtained by the BET nitrogen method is much lower
than for a sample regenerated at 350C (Table 2 , sample-
Alcan AA200C). At a regeneration temperature of 450C
the pore surface area is reduced to less than 244 m/g due
to sintering or as a result of formation of a different transi-
tion alumina associated with lower specific area. A sample
repeatedly regerated at 350C (Table 2 , sample-Alcan
AA300) showed little loss in the specific surface area and
the amount of water removed was equivalent to monolayer
coverage. 350C was therefore selected as the most suitable
temperature for the dehydration of most of the commercial
activated alumina samples. The exact optimum temperature
for a particular sample will be slightly different depending
on the type and composition of the transition aluminas.
ADSORPTION
ISOTHERMS
The equilbrium capacities calculated from breakthrough
curves were compared with those obtained by the gravimetric
method. The results are quite consistent as may be seen from
Figure 2.
70 I
 0

"
A O P

~GravimetricData.
6 Breakthrough Curve Daia.

0 1
0
. . . ,
666.5
I . .

1333.5 1999.5
I
P (Pa)
Figure 2 - Comparison of breakthrough and gravimetric data for
adsorption of water vapour on activated alumina (Alcan AA200C)
at 105C.

1
o Adsorption Isotherm Pore radius (A)
A Desorption Isotherm
Figure 5 - Pore size distribution for Alcan AA300 activated
alumina.

@Favourable Zone I
Appr point of inflection
1 I 1 1 I
0 666.5 1333.0 1999.5 2666.0 3332.5 I '

P (Po)
J
Figure 3 - Adsorption and desorption isotherms for Rhone- t ' I

,I
" A I c m PSA I1 A l c m PSA I Alcsn IDBBOiO5
Poulenc activated alumina at 26C.
----L - 1 .
I
I I 1 1
I 500
P (Pa)
1000 1500 2000

Figure 6 - Isotherms at 26C for water vapour on activated alu-

0 I
1 I
0 666.5
Figure 4 - Adsorption and desorption isotherms for Alcan AA300
activated alumina at 24C.
Representative water vapour adsorption isotherms span-
ning the entire range of concentration from zero to satura-
tion are shown in Figures 3 and 4. The isotherms for both
samples are very similar and are of Type I1 from (in the
Brunauer classification). This is typical of adsorbents which
have a wide distribution of pore size where there is con-
tinuous progression from multilayer adsorption to capillary
condensation, which causes the rapid increase in loading as
the saturation vapour pressure is approached. The onset of
significant capi[lary condensation corresponds to a pore
diameter of 37 A (Figure 5). The Rhone-Poulenc activated
alumina sample has a bi-modal micropore size distribution:
702
mina. Comparison of different alumina samples.
the first peak corresponds to a pore di9meter of 20 A , the
second to a pore diameter of 40 to 50 A . Substituting these
values in the Kelvin equation together with the physical
properties for water at 298K (V, = 18 cm'/mol, CT\ =
72.75 x N/m, 8 = 0) suggests that the onset of con-
densation will occur at p / po = 0.35 for the Rhone-Poulenc
sample and p / p o = 0.45 for Alcan AA300.
1 I I
13330 19995 2666.0 3332.5 ANALYSISOF WATER VAPOUR ISOTHERMS
P (Pa)
Experimental isotherms for several different activated alu-
mina samples measured under comparable conditions are
shown in Figure 6 . Each sample is briefly described in
Table I . It is clear that there are substantial differences in
capacity. The differences in the water capacity can arise
primarily from
i) Dehydration conditions.
ii) Differences in pore size distribution and surface area.
iii) Differences in the surface chemistry of the phases
produced in the activation step.
In order to resolve these differences, a detailed series of
isotherm measurements was undertaken. After adsorption,
the sample was desorbed in steps to measure the desorption
isotherm. The adsorption and desorption isotherms for
Rhone-Poulenc and Alcan-AA300 activated alumina samples
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, AUGUST. 1092
 0- 301 I
I
I I I
I

.......
i. j +HOH
251 d
0

4
.. ,,,
I ,
I ,

... ,.
. Chemisorption
.
I
,
,

OH OH
I I I I I I
0 666.5 1333.0 1999.5 2666.0 3332.5
P (Pa)
.......
I i +HOH Figure 8 - Decoupled isotherms for water vapour on Rhone-
.,
I

I
*.
.
,

Poulenc activated alumina at 6C. (1) chemisorption isotherm; ( 2 )

I ,

,,
I
. I
,
Quasichemisorption and (3) physisorption isotherms with hysteresis loop due to capil-
lary condensation; (4) initial composite adsorption isotherm.
I ,

i4
H,
0 '0
I
-.-.--o A-0- A-0-
/I\ /I\
Figure 7 - Representation of the chemisorption of water molecules
o n an activated alumina surface.
are shown in Figures 3 and 4. The desorption isotherm does
not retrace the original adsorption isotherm but rather it lies
substantially above it. Thus, when the sample was evacu-
ated to zero pressure of water vapour (1 mPa), at the meas-
urement temperature, the initial dry weight was never
recovered. A certain amount of water was retained on the
sample so that a hysteresis loop is formed between the adsorp-
tion and desorption curves persisting down to zero water
vapour pressure. The question that arises is: how much water
is associated with this loop? Clearly, this loop is quite
different from the hysteresis lop which is formed at high pres-
sure as a result of capillary condensation. Does the water
associated with the low pressure hysteresis loop corresponds
to the chemisorbed water or the quasicheisorbed water? In
order to answer these questions it is necessary to have a clear
understanding of the difference between the chemisorbed and
quasichemisorbed water.
A regenerated sample of activated alumina will have both
acidic and basic defect sites as well as acidic and basic
hydroxyl groups. The initial contact of water vapour with
a surface will lead to chemisorption involving dissociation
of the water molecule into H and OH - ions which attach
+
to surface sites. The sites for these ions can be oxide ions
on the outermost surface layer and an incompletely coordi-
nated aluminum ion in the next layer or an exposed cation
located in a hole that is electron deficient and acts as an acid
site. Thus chemisorption of water involves more than one
type of site. The simplest representation of water chemisorp-
tion o n activated alumina surface is given in Figure 7, in
which a Lewis acid site is hydroxylated and a Brdnsted base
(0-)is protonated by reactions involving only the outer
layer. Thus chemisorbed water is not in molecular form.
Quasichemisorption involves molecular water that is
hydrogen bonded to hydroxyl groups on the activated alu-
mina surface. Five types of hydroxyl groups can occur on
0 666.5 1333.0 19995 26660 33325
P (Pa)
Figure 9 - Decoupled isotherms for water vapour o n Alcan
AA300 activated alumina at 24C. ( I ) chemisorption isotherm: (2)
and (3) physisorption isotherms with hysteresis loop due to capil-
lary condensation; (4) initial composite adsorption isotherm.
the surface of the activated alumina (Details concerning these
hydroxyl groups and their net charges are explained by
Knozinger and Ratnasamya, 1978). Obviously, only acidic
surface hydroxyls will form strong hydrogen bonds with
water molecules and the strength of the bond can be expected
to increase with the charge on the hydroxyl. Thus a hydroxyl
group having a +0.5 net charge will hold a water molecule
more strongly than a hydroxyl having a net positive charge
of only +0.25. The hydrogen bonded structures are quite
stable against dissociation at ordinary temperatures. Thus,
from the above definitions of chemisorbed and
quasichemisorbed water, one can say that both these forms
may contribute to the low pressure hysteresis loop since in
both cases the water molecules are strongly held and the
available sites will be fully occupied in the low pressure
range.
The components of the chemisorption isotherm were
resolved in the following way. The Initial adsorption isotherm
(curve 4 in Figures 8 and 9) is assumed to represent the super-
position of the chemisorption, quasi-chemisorption plus phys-
ical adsorption isotherm. The initial desorption isotherm,
below the inflection point, reflects the sum of the quasi-
chemisorbed and physisorbed water plus irreversibly
chemisorbed monolayer. The later is taken to correspond to
the residual water remaining after prolonged evacuation at
1 mPa and isotherm temperature. Subtracting this residue
from the initial composite desorption curve yields curve ( 3 )

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 70, AUGUST, 1992 703
representing the quasi-chemisorbed, physically adsorbed and
condensed water. The difference between the initial adsorp-
tion curve (curve 4) and curve ( 3 ) (below the inflection curve)
yields the chemisorbed water (curve 1). The difference curve
+
3 curve 1 - curve 4 represents the capillary condensa-
tion. The difference between the initial desorption and
adsorption curves (Figure 3 and 4) represents the sum of
capillary condensation plus the chemisorbed saturation limit
minus the actual chemisorption. The subsequent adsorption-
desorption curves, repeated without high temperature
regeneration, follow curves 2 and 4 (Figure 8 and 9) showing
the well defined hysteresis loops characteristic of cdpillary
condensation. It is seen that these loops belong to the H4
category of the IUPAC classification (Gregg and Sing, 1982).
MODELLING
OF THE INDIVIDUAL ISOTHERMS
The chemisorption isotherms are clearly of the normal
Type-I form (in the Brunauer classification) while the phys-
isorption isotherms show the characteristic BET (Type 11)
form. As chemisdrption is limited to the monolayer region
one may anticipate that the chemisorption isotherm should
approximate the Langmuir model (Ruthven, 1984):
q/q.\ = bp/(l + bp) . . . . . . . . . . . . . . . . . . . . . . . .
or
p i q = llbq,y + p l q , . . . . . . . . . . . . . . . . . . . . . . .
Langmuir plots (p / q vs p ) are found to be approximately
linear (Figure 10) confirming that this expression is indeed
a reasonable representation of the chemisorption isotherms.
The derived parameters are summarized in Table 3.
According to the Langmuir model of the value of qs should
correspond to monolayer coverage and should therfore be
substantially independent of temperature, while b should vary
with temperature in accordance with the normal vant Hoff
equation:
b = b,, exp(-AHIRT) ......................
It is seen from Table 3 that the values of qs obtained at
different temperatures are indeed almost constant for all the
samples. Thus the data obtained for all samples conform to
the expected behaviour and yield a value of about - 84 Hlmol
for the (exothermic) heat of chemisorption. This appears
reasonable in comparison with th isosteric heat (for phys-
ical adsorption at higher loadings) of about 46 kJ/mol and
the heat of evaporation (about 42 kJ/mol).
The reversible portion of the physisorption isotherms (over
the entire range of concentration) follows, approximately,
the BET model (Ruthven, 1984):
or
+ (bp/p,))] / [bq,] . . . . . . . . . . . . . . . . . . . . .
704 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING. VOLUME 70. AUGUST. 1902
1200,
800
P
5 800
&
s?
400
200
1 _ .
0 200 400 600 800 1000
I (ra)
Figure 10 - Langmuir plot for chemisorbed water vapour on
Alcan ID880105 activated alumina at 57C.
BET plots ( p / q [ p o - p ] vs p l p , ) for the physisorption
isotherms were made and the monolayer capacity q,,, for
physisorbed water was calculated from the slope and inter-
cept of these plots. These values for various samples are
shown iq Table 3. The nominal area of a water molecule
(2)
.
is 11.7 A The surface areas, estimated on this basis from
the values of q, derived from the BET fit of the water phys-
isorption isotherms are included in Table 3. These values
are consistently about 42% of the BET nitrogen areas,
indicating that the water molecules in the first layer are prob-
(3) ably not close packed on the surface.
The Henry constants for water vapour in activated aluminas
were obtained from the virial plots as explained by Ruthven
(1984). The limiting heats of adsorption (within the Henrys
Law region, i.e. at sufficiently low concentration, in the
linear range of isotherm) were calculated from the Henry
constants at different temperatures using the vant Hoff
equation.
K = KO exp(-AHIRT) ...................... (8)
(4)
The limiting heats of adsorption for the different samples
are summarized in Table 4. Isosteric heats of adsorption were
calculated using the Clausius-Clapeyron equation (Ruthven,
1984) for the reversible physisorbed isother. Figure 1 1 shows
the variation of heat of adsorption with loading. The values.
even at higher loadings, are significantly higher than the
latent heat of evaporation ( = 42 kJ/mol).
Conclusions
Adsorption of water vapour on activated alumina involves
several different mechanism. The experimentally observed
equilibrium isotherms represent the sum of the contributions
from chemisorption, quasichemisorption, physical adsorp-
tion and capillary condensation. Samples of activated alu-
mina differ in their defect structure as well as in their surface
area and pore size distribution. To understand the resulting
differences in the adsorptive properties and to correlate the
isotherm data in a rational and fundamental way it is neces-
sary to separate the contributions from the various
mechanisms rather than attempting to correlate and compare
(6) directly the composite isotherms.
 TABLE3
Summary of Parameters Derived from Physisorption and Chemisorption Data

RP A-grade 26 3.25 lo6 360 3.80 149

RP A-grade 54 3.25 1.2 x lo5 3.41
RP A-grade 100 3.25 8 X lo3
PSA-I 26 3.25 8 x lo5 38 1 4.11 161
PSA-I 105 3.13 6 x lo3 2.80
PSA-I1 26 9.76 9.0 x 10' 385 4.66 182
PSA-I1 54 8.60 4.3 x lo5 4.25 170
AA 100 26 3.12 7.15 x lo5 4.20 I65
AA200X 29 3.45 8.74 x lo5 38 1 4.20 I65
ID880 I05 26 2.50 1.66 x lo5 2.30 90
ID880 105 57 I .05 1.53 x lo4
AA 300 26 5.00 3.0 X lo6 325 141

*Dimensionless basis.

TABLE4 other hand if a very low humidity level is required this can
Limiting Heat of Adsorption for Various Activated Alumina only be achieved within the chemisorption region, and a
Samples much higher regeneration temperature is required.
Sample - A H , , (kJ/mol)
Acknowledgement
Rhone-Poulenc 77.9
Alcan PSA-I 49.8 This work was carried out as part of a CRD project, jointly funded
Alcan PSA-I1 57.4 by Alcan Ltd. and the Natural Sciences and Engineering Research
Alcan ID880105 79.6 Council of Canada. This support is gratefully acknowledged.

Nomenclature
b = Langmuir equilibrium constant, cm'imol
70 II 1
b , = pre-exponential factor in b , cm'/mol
b' = BET equilibrium constant, dimensionless
c = fluid phase concentration, molicm'
Co = final steady state value of c, mol/cm3
d = pore diameter, cm
A H = heat of adsorption, k.T/mol
K = Henry constant, dimensionless
L = length of adsorbent bed, cm
P = sorbate partial pressure, Pa
Latent Heat of Evaporation
Po = saturation vapour pressure of liquid phase, Pa
9 = solid phase concentration, g/lOO g
30
40 = value of q in equilbrium with c,,, g/l00 g
0 2 4 6 8 10 4s = monolayer coverage, g/IOO g
R = gas constant, J/mol . K
Loading (g/100 g)
s = specific surface area, cm'ig
Figure 11 - Variation of heat of adsorption with water loading s, = BET surface area by use of water sorbate. cm'ig,
for Rhone-Poulenc activated alumina. s, = BET surface area by use of nitrogen sorbate. cm-/g
-
t = mean retention time, s
T = absolute temperature, K
The behaviour of the individual isotherms is straightfor- v = interstitial fluid velocity, cm/s
ward and conforms to simple idealized models (Langmuir v,,, = molar volume of sorbate, cm7/mol
for chemisorption, BET for physisorption) and the vp = pore volume, cm3/100 g
parameters calculated from these models agree well with
Greek letters
independently measured values such as the specific area and
the limiting heat of adsorption. There are two hysteresis E = bed voidage
loops: the well known loop at higher relative pressure arises Cl = defined in Equation (7)
from the capillary condensation while the low pressure hys- us = surface tension, N/m
teresis loop results from irreversibility of the chemisorption 8 = contact angle, degrees
isotherm.
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