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Adsorption (2008) 14: 241246

DOI 10.1007/s10450-008-9106-0

Adsorption and diffusion of propane and propylene


in Ag+ -impregnated MCM-41
F. Iucolano P. Aprea D. Caputo C. Colella M. Eic
Q. Huang

Received: 2 May 2007 / Revised: 27 November 2007 / Accepted: 29 January 2008 / Published online: 20 February 2008
Springer Science+Business Media, LLC 2008

Abstract Equilibrium data and diffusion characteristics of


propane and propylene were determined on mesoporous adsorbents modified with an organic molecule (APTES) and/or
impregnated with AgNO3 , in order to obtain a separation by
adsorption via -complexation.
Adsorption capacities were determined by a gravimetric technique, while diffusion characteristics were evaluated by the ZLC technique. The equilibrium isotherms data
showed that the modification with an organic molecule will
weaken the -interaction between Ag+ and double C=C
bond. On the other hand slightly higher adsorption capacities for propylene (about 1.5 mol/kg) were obtained for
the sample prepared by a direct impregnation with larger
amounts of AgNO3 (M4 sample).
Diffusion runs confirmed that the propane desorption rate
on M4 sample was much higher compared to propylene.
This evidence leads to a potential application of that adsorbent material for a kinetic separation.
Keywords Propane Propylene MCM-41 Adsorption
Diffusion Separation

1 Introduction
Propane-propylene separation is one of most important and
most expensive operations in the chemical and petrochemiF. Iucolano () P. Aprea D. Caputo C. Colella
Dipartimento di Ingegneria dei Materiali e della Produzione,
Universit Federico II, Napoli, Italy
e-mail: iucolano@unina.it
M. Eic Q. Huang
Department of Chemical Engineering, University of New
Brunswick, Fredericton, Canada

cal industry. Propylene feedstock, used for the production of


polypropylene, requires a purity of at least 99.5%, normally
achieved by distillation in large plants. The high cost of this
operation, due to the small separation factor of the two molecules, having approximately the same size and similar boiling points, prompted a number of investigations searching
for unconventional techniques in the recent years (Padin et
al. 1999; Padin and Yang 2000; Grande et al. 2004). At the
present time adsorption appears to offer a suitable alternative
to distillation, as it makes possible to increase the separation
factor and therefore reduce the cost of the process (Ruthven
2000).
Among the many commercial adsorbents tested, mesoporous materialscharacterized by large specific surface areas, narrow pore size distribution, adaptable pore size and
possibility to be modified and functionalizedseem to be
promising candidates for this kind of separation.
In order to improve the olefins/paraffins separation efficiency, an useful procedure consists of spreading out metal
cations, such as Ag+ or Cu+ , over the mesoporous internal
surface, making it possible the formation of -complexes
between a cation of adsorbent and a double C=C bond of
a sorbate (Padin and Yang 2000; Takahashi et al. 2002;
Grande et al. 2004; Basaldella et al. 2006). Separation by
adsorption via -complexation is a sub-group of adsorption
reactions, characterized by bonds stronger than the Van der
Waals forces alone, and therefore achieving high selectivity
regarding olefins separation from the mixtures. On the other
hand, this type of bond is still sufficiently weak, thus allowing regeneration to be performed by raising temperature
and/or decreasing pressure.
The aim of this work was to investigate the adsorption
features of suitably modified MCM-41 mesoporous silica, in
order to evaluate possible application in propylene/propane
separation process.

242
Table 1 Textural properties and
Ag content (%) of MCM-41
samples

Adsorption (2008) 14: 241246


SBET

Vpores at P /P0 = 0.8

Dpores

Ag content

(m2 /g)

(cm3 /g)

()

(%)

M1

423

0.39

32

9.26

M2

382

0.43

30

8.92

M3

757

0.45

35

2.98

M4

793

0.49

36

6.03

Sample

2 Experimental
2.1 Materials
MCM-41 mesoporous silica impregnated with AgNO3 at
different amountswith or without a preliminary modification with 3-aminopropyltriethoxysilane (APTES)were
synthesized as powders, with a procedure described in one
of our earlier studies (Aiello et al. 2006).
M1 and M2 samples are MCM-41 mesoporous samples
impregnated with different amounts of AgNO3 after a preliminary modification with APTES, while M3 and M4 were
obtained with a direct impregnation with different amounts
of AgNO3 (Aiello et al. 2006).
The spreading of Ag+ on mesoporous substrate was accomplished using the wet impregnation technique. Accordingly, a sample of MCM-41 was contacted with an aqueous
solution of the salt to be dispersed along a time sufficient for
its mesopores imbibition. Then the sample was recovered
and heated for 4 h at 105 C in air to remove water.
All the samples were characterized by nitrogen adsorption-desorption isotherm analysis (Micromeritics ASAP
2010 apparatus) and X-ray dispersion analysis (JSM-T330A
Scanning Microscope).
Main textural properties and Ag amounts of all the adsorbents tested are reported in Table 1.
2.2 Adsorption equilibrium measurements
The adsorption properties of the mesoporous materials were
investigated from the equilibrium isotherms of propane and
propylene at 20 C. Experimental adsorption data were collected by means of a gravimetric technique, using a McBaintype balance (detailed description has been reported in
Caputo et al. 2004).
2.3 Diffusion measurements
Diffusion measurements for propane and propylene were
performed using the ZLC (Zero Length Column) chromatographic technique (Eic and Ruthven 1988). A very small
amount (1.52.0 mg) of adsorbent was placed in the ZLC
column and equilibrated with sorbate diluted in a helium
flow, to obtain a low concentration required by the ZLC

theory. The desorption was performed by purging with helium at a flow rate high enough to minimize external mass
and heat transfers. Essentially the same diffusion parameters were extracted from the experimental runs under various
purging flow rates, thus confirming kinetically controlled
process. A purge flow rate of 30 cm3 (STP)/min helium was
selected as a standard flow rate for all experiments in this
study. The effluent sorbate concentrations from the ZLC column were measured using a gas chromatograph (HP 5900)
equipped with a FID detector. Details of the experimental
method have been described elsewhere (Eic and Ruthven
1988; Jiang and Eic 2003).

3 Theory
The analysis of the ZLC desorption curve involves solving Fickian diffusion equation with appropriate initial and
boundary condition, i.e., zero concentration of sorbate
species on the surface of the adsorbent particle (Eic and
Ruthven 1988). For a linear equilibrium system with uniform spherical particles the normalized effluent gas concentration is given by:


c
2L
exp(n2 Dt/R 2 )
=
2
co
[n + L(L 1)]

(1)

n=1

where n are eigenvalues given by the root of the equation:


n cot n + L 1 = 0

(2)

and
L=

R2
1
1 purge flow rate R 2
=
3 (1 )z KH D 3 crystal volume K H D

(3)

In (3) is the voidage of the ZLC bed, the interstitial gas


velocity, z the ZLC bed depth, t the time of purging, KH
the dimensionless Henrys Law constant and D/R 2 the diffusion time constant.
For the long time case, (1) can be reduced to a simple exponential decay curve, since only the first term of the summation is significant:
c
exp(1 Dt/R 2 )
= 2L 2
co
[1 + L(L 1)]

(4)

Adsorption (2008) 14: 241246

243

Fig. 1 Propylene (!) and propane (") adsorption isotherms on M1M4 samples at 20 C

A plot of ln(c/co ) versus t should produce a linear asymptote in the long time region, and from the slope and intercept
the parameters D/R 2 and L can be extracted.

4 Results and discussion


4.1 Adsorption equilibrium isotherms
The adsorption isotherms at 20 C showed that all the samples exhibited a greater adsorption capacity for propylene
compared to propane (Fig. 1), and such a behaviour was
more evident for the samples M3 and M4, impregnated with
AgNO3 without a preliminary modification with APTES.
Adsorption capacities at 1 atm (760 Torr) for propylene
in M1M4 samples were 1.25, 0.70, 1.23, 1.54 mol/kg,
respectively, and those for propane were 1.00, 0.55, 0.69
and 1.02 mol/kg, respectively. The increased adsorption capacity for propylene is attributed to the presence of Ag+

ions for -complexation. Although M3 was loaded approximately with only a half amount of Ag+ content compared
to M4, its adsorption capacity at 1 atm for propylene was
80% of M4. This suggests that there is an optimum loading of Ag+ for propylene adsorption, which is between 3%
and 6%.
Nevertheless, in general, the adsorption capacities for
propylene were lower than expected. They were comparable
or even smaller than on a silver-based MCM-41 measured
at 70 C (Padin and Yang 2000). This may be related, either
to the inactivation of Ag+ by reduction to Ag0 or formation
of Ag2 O (also the formation of this oxide reduces the possibility of -complexation between Ag+ and the olefin double bond, resulting in a lower adsorption capacity for propylene), or to the degradation of the organic functional group
(M1 and M2 samples), with consequent deactivation of the
adsorbent materials.
The equilibrium selectivities (expressed as the propyleneto-propane adsorption capacity ratio) versus the pressure,

244

Fig. 2 Propylene/propane equilibrium selectivity at 20 C for M1 (!),


M2 ("), M3 (1) and M4 (2) samples

are reported in Fig. 2. M3 and M4 samples show higher


values than M1 and M2, revealing that the modification of
APTES doesnt enhance the separation factor of propylene
over propane. All the adsorbents appear to be rather selective at low pressure values, with a quick decrease of selectivity at higher pressures. Such a dependence on the driving
force indicates that, together with the formation of Ag+
bonds, the steric effect plays an important role in the separation mechanism.
4.2 Diffusion results
The ZLC measurements were performed for propane and
propylene in a temperature range of 35 to 75 C. The concentration of the sorbate in helium was set at 0.2 vol. %,
which is low enough to ensure that the ZLC experiments
were carried out in the linear region of isotherms as required.
Figure 3 shows the desorption curves for all the samples, while diffusion time constants for propane and propylene obtained from the long time region of ZLC curves and
the corresponding activation energies are summarized in Table 2. It is clear that propane has higher values of diffusion
time constants than propylene.
Table 2 also shows that M2 sample has an activation energy for diffusion higher for propane than propylene, which
may appear unusual remembering that electrons from unsaturated HCs should provide stronger interaction with the
active sites of an adsorbent surface ( complexation), thus
increasing activation energy.
Nevertheless, as discussed in the previous paragraph, the
comparable adsorption capacities exhibited by M2 sample
toward propane and propylene (see Fig. 1) suggest a possible deactivation of the adsorbent material. Therefore the

Adsorption (2008) 14: 241246

unexpected values of activation energies are probably due


to the fact that the adsorption mechanism of propylene on
M2 sample is no more strongly related to a -complexation
with Ag+ cations but (as for propane) essentially based on
van der Waals-type interactions with mesopores walls.
From the ZLC curves, it appears that the propane desorption rate is strongly dependent on the sample type, e.g., both
M1 and M4 samples (obtained using a higher Ag amount in
the reaction batch) show a very fast decrease in the propane
concentration, whereas the desorption is much slower for
M2 and M3 samples. The desorption rates for the M4 sample
were faster than those for M1 sample, and all of them were
so fast that no ZLC analysis was possible. Furthermore, for
all the samples the desorption rate increases with the temperature.
The adsorption behaviour involving propylene was somehow different, e.g., the ZLC curves showed that the diffusion
rates were almost the same for M1, M2, M3 samples, indicating that the modification carried out by APTES had not
changed the adsorption kinetics of propylene.
The dependence of the diffusion rate on the temperature is quite modest for M1M3 samples. On the contrary,
M4 sample exhibited a desorption rate for propylene significantly lower and more dependent on the temperature,
i.e., higher activation energy (around 30 kJ/mol). The activation energy for diffusion of propylene in M4 sample is
comparable with the heat of adsorption of same species in a
silver-based -complexation mesoporous silica with cylindrical pores, which was found to be 34 kJ/mol (Grande et al.
2004). This suggests that the transport of propylene in M4
sample appears to be mainly controlled by mesopore diffusion (Vinh-Thang et al. 2006).
Concerning the ability to separate propane from propylene by means of a diffusion process (kinetic separation),
the M2 and M3 samples do not seem to be the good candidates. As can be seen from the collected data, the behaviour of those samples towards both sorbates is essentially
the same. On the other hand, M4 sample shows the maximum difference with regard to mass transfer rates of propane
and propylene, thus suggesting the possibility of using this
sample for the kinetic separation of these sorbates. Related
to this, M1 sample exhibits the second largest difference in
mass transport behaviours for the sorbates, and as such could
also be considered for the kinetic separation.
The above mentioned results indicate that the presence of
an organic molecule within the mesopores can weaken the
-interaction between Ag+ and double C=C bond, while
the more promising behavior of M4 sample compared to M3
and M2 may be related to a larger amount of Ag+ present in
its mesopores.

Adsorption (2008) 14: 241246

245

Fig. 3 Experimental ZLC curves for propane (left) and propylene (right) in M1, M2, M3, M4 samples

5 Conclusions

Nomenclature

The experimental data provide a good overview of the equilibrium and diffusion behaviour of MCM-41 impregnated
with AgNO3 , either modified with APTES or not. Equilibrium results are not conclusive with respect to a use of investigated samples for thermodynamic separation of propane
and propylene, due to the modest adsorption capacity for
both sorbates and the varied selectivity, which is high at very
low pressure, but quickly diminishes at the higher pressures.
However, kinetic separation appears to be more promising
based on the different diffusion behaviour of the sorbates in
the material: in particular, propane demonstrated a very high
diffusion rate in the M4 sample (MCM-41 impregnated only
with AgNO3 at higher content), while propylene was shown
to be slow, indicating a possibility for the successful application.

c=
c0 =
L=
n =
D=
t=
R=
T =
=
=
z=
KH =

sorbate concentration, mol/m3


initial sorbate concentration, mol/m3
constant defined in (3), dimensionless
eigenvalue: roots of (2), dimensionless
intracrystalline diffusivity coefficient, m2 /s
time, s
particle radius, m
temperature, K
voidage of the ZLC bed, dimensionless
interstitial gas velocity, m/s
bed depth, m
Henrys law constant, dimensionless

246

Adsorption (2008) 14: 241246

Table 2 Diffusivity data and activation energy for propane and propylene in M1, M2, M3, M4 samples
Propane
T (C)
M1

M2

M3

M4

Propylene
D/R 2 (s1 ) 103

E (kJ/mol)

T (C)

D/R 2 (s1 ) 103

35

35

2.05

45

55

2.39

60

75

2.71

35

1.55

35

1.49

55

2.16

14.43

55

1.76

75

2.96

75

2.44

35

3.12

35

1.85

55

4.25

10.12

55

2.41

75

4.91

75

3.11

35

35

0.43

55

55

0.83

75

75

1.59

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