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DOI 10.1007/s10450-008-9106-0
Received: 2 May 2007 / Revised: 27 November 2007 / Accepted: 29 January 2008 / Published online: 20 February 2008
Springer Science+Business Media, LLC 2008
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
242
Table 1 Textural properties and
Ag content (%) of MCM-41
samples
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
(2)
and
L=
R2
1
1 purge flow rate R 2
=
3 (1 )z KH D 3 crystal volume K H D
(3)
(4)
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.
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
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 =
246
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)
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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