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The methane steam reforming in a catalytic membrane reactor has been studied. A previous
theoretical study of this reaction has been carried out. In the model a global kinetic rate as
function of three reactions over nickel catalyst as proposed by Xu and Froment (AIChE J. 1989,
35 (1), 88-96, 97-103) has been considered. It has been shown that the counterflow configuration has, at high temperature (500 C), a marginal advantage on parallel flow and, also, that
the space velocity cannot be considered a design variable for membrane reactors. A laboratory
plant was realized utilizing membranes of Pd and Pd/Ag supported on Al2O3. The Pd membranes
utilized have been prepared using the co-condensation technique and the electroless plating
method. A comparison of the overall membrane performance has also been carried out. The
experiments were aimed to study the effects of several parameters such as temperature, feed
flow rate, and feed molar ratio on the methane conversion. The experimental results have been
compared with the data predicted by the previously developed theoretical model.
Introduction
In the last few years the interest for innovative
solutions, in industrial and chemical processes, has been
focused on membrane reactors (Falconer et al., 1993;
Zaman and Chakma, 1994; Saracco and Specchia, 1994).
One of the most important advantages of these kinds
of reactors is the possibility of overcoming the limitation
imposed by the thermodynamic equilibrium.
To remove hydrogen from the reaction volume, it is
possible to use palladium and its alloys, permeable only
by hydrogen. Techniques have been developed aimed
at depositing a small amount of Pd over porous supports: chemical vapor deposition (Morooka et al., 1995),
electroless plating (Shu et al., 1993), sputtering, and
solvated metal atom deposition (Capannelli et al., 1993;
Basile et al., 1996). In this way, it is possible to reduce
the thickness of the membrane with the advantages of
lower costs and of higher permeability. The durability
of the Pd membranes, which are highly fragile after
thermal excursions in the presence of hydrogen, is,
however, a significant problem. In order to overcome
this drawback, Pd/Ag (Gobina et al., 1995) and other
alloys have been used.
The hydrogen and syngas productions are two of the
most important processes for chemical industry. About
50% of hydrogen demand is actually satisfied by means
of the methane steam reforming (MSR) reaction, due also
to increased natural gas production (mainly methane).
Methane steam reforming involves five species in
three reversible reactions.
CO + H2O ) CO2 + H2
Reaction side
1000Wcat
dNi
)
Membrane Preparation
Membranes used in this work are based on a very thin
dense film of Pd or Pd-Ag alloys deposited on a tubular
support of alumina, with two different techniques:
electroless plating (EP) (Shu et al., 1993) and solvated
metal atom deposition (SMAD) (Capannelli et al., 1993;
Basile et al., 1996). The first technique allows the
deposition of the metallic film on the external surface
of the support. With the second one the deposition can
be carried out also on the inner surface of the tubular
support.
Electroless Plating (EP). The thin metallic film
has been obtained with a modified electroless technique.
The film is a Pd-Ag (79/21%) alloy, 10 m thick, with
a low defects concentration and homogeneous surface,
ensuring a significant separation factor between hydrogen and the other gaseous components before the
reaction tests. Such a composite structure shows a
remarkable capacity to operate at high temperature.
The film has been obtained by means of the electroless
plating technique because of the applicability of such a
technique to obtain layers of different metals having
different thicknesses. The electroless deposition can be
dz
60Vr
i, jrj - H Pd
i
j)1
Ar
Permeation side
dNi
) (H Pd
i
dz
Ar
where Wcat is the catalyst weight, Vr is the reaction
volume, Ar is the cross section of the reaction side, is
the membrane diameter, i,j is the reaction coefficient,
and z is the reactor axial position; the + sign is used
for the parallel-flow configuration and the - sign must
be used for the counterflow configuration.
Only the hydrogen balance equations (i ) H2) (reaction and permeation side) have the permeation term
Pd
HPd
is equal to
i . For the other species the term Hi
zero. The traditional reactor model is obtained from the
present model by assuming no permeation even for
hydrogen.
The set of differential equations has been solved
numerically by a fourth-order variable step RungeKutta method; for counterflow simulation the shooting
method has been used.
H2/CH4
CO/CH4
CO2/CH4
2.61
0.87
3.07
1.85
1.79
0.58
Figure 5. Methane conversion versus temperature: (a) experimental data for the SMAD membrane; (b) model results; (c)
equilibrium. Pr ) Pp ) 101 kPa, Qr ) 98 SCCM, Qp ) 53.2 SCCM,
and m ) 4.
Acknowledgment
The authors are grateful to Prof. G. Vitulli of the
University of Pisa, Pisa, Italy, for the helpful discussion
and preparation of the SMAD membrane and to Dr.
Carlo Cavenaghi of the Hengelhard de Meern BV,
Milano, Italy, for the catalyst supply.
Nomenclature
Figure 7. Model results for several sweep gas flow rates: (a) Qp
) 500 SCCM; (b) Qp ) 200 SCCM; (c) Qp ) 53.2 SCCM. The
experimental results (circles) for a SMAD membrane are also
reported (see Figure 2). T ) 536 C, Pr ) Pp ) 101 kPa, and m )
2.5. The solid square represents the equilibrium value.
A ) area [cm2]
HPd ) molar flux through a Pd membrane [mmol cm-2
min-1]
m ) H2O/CH4 molar feed ratio
N ) molar flux [mmol cm-2 min-1]
P ) pressure [Pa]
Q ) flow rate [SCCM ) cm3 (STP) min-1]
r ) reaction rate [mol (g of catalyst)-1 h-1]
S ) space velocity [SCCM (g of catalyst)-1]
T ) temperature [C]
V ) volume [cm3]
Wcat ) catalyst weight [g]
z ) reactor axial position [cm]
H298 ) reaction heat [kJ mol-1]
) Pd-membrane outer diameter [cm]
i, j ) reaction coefficient
Superscripts and Subscripts
0 ) initial conditions or reference value
p ) permeation side
r ) reaction side
i ) species i
j ) reaction j
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