Ind. Eng. Chem. Res.

1997, 36, 3369-3374

3369

Methane Steam Reforming Analysis in a Palladium-Based Catalytic

Membrane Reactor
Giuseppe Barbieri,, Vittorio Violante, Francesco P. Di Maio,|
Alessandra Criscuoli,| and Enrico Drioli*,,|
CNR, Institute of Research on Membranes and Chemical Reactors Modelling, C.da Arcavacata,
87036 Rende (CS), Italy, CR ENEA Frascati, Frascati (RM), Italy, and Department of Chemical Engineering
and Materials, University of Calabria, C.da Arcavacata, 87036 Rende (CS), Italy

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.

CH4 + H2O ) CO + 3H2

H298 ) 206 kJ mol-1

(1)

CO + H2O ) CO2 + H2

H298 ) -41 kJ mol-1

(2)

* Author to whom correspondence should be addressed.

CNR.
Phone: +39 984 492039. Fax: +39 984 402103. E-mail:
barbieri@area.cs.cnr.it.
CR ENEA Frascati.
| University of Calabria.
S0888-5885(97)00033-X CCC: $14.00

The reforming reaction (1) is thermodynamically

favored by high temperature and low pressure. The
second reaction, water-gas shift (WGS), does not depend on pressure and is favored by low temperature.
Heat developed by reaction (2) is not sufficient for the
thermal needs of the process, as can been seen from the
overall reaction:

CH4 + 2H2O ) CO2 + 4H2

H298 ) 165 kJ mol-1

(3)

The overall reaction (3) is endothermic and limited

by equilibrium; it needs high temperature to obtain
reasonable industrial conversion. Traditionally the
industrial converters are made of hundreds of parallel
tubes contained in furnaces and operating at 850 C to
obtain a degree of methane conversion of around 80%.
The catalyst used is Ni/alumina and is packed inner
tubes.
This reaction has been widely studied in the traditional systems.
The catalyst that showed more efficiency for MSR
reaction is the Ni/alumina, as reported by Xu and
Froment (1989a,b). Their kinetic analysis, in a traditional reactor, has been made in the temperature range
573-823 K and for pressure varying from 300 to 1000
kPa. This kinetic model is based on the LangmuirHinshelwood mechanism and involves 13 steps that lead
to the three global reactions reported above.
Recently various papers on MSR in a catalytic membrane reactor (CMR) appeared in the literature. Tsotsis
et al. (1992) have studied MSR in a porous catalytic
membrane reactor in the temperature range 200-600
C. Hughes (Adris et al., 1991) studied the behavior of
MSR reaction in a fluidized bed. Uemiya et al. (1990)
utilized a Pd-membrane reactor to study the same
reaction. Laegsgaard et al. (1995) have analyzed the
carbon deposition over catalyst, in a Pd-Ag membrane
reactor, for the MSR reaction; in membrane reactors a
higher steam/methane ratio than those in traditional
ones has to be used to avoid the carbon formation due
hydrogen removal from the reaction volume. Shu et al.
(1993) showed that using Pd and Pd-Ag membranes
for MSR reaction, it is possible to enhance the conver 1997 American Chemical Society

3370 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

sion of methane by removal of hydrogen, also at mild

operating conditions. Bredesen and Sogge (1996), studying the production of hydrogen and syngas by means of
natural gas transformations, showed that membrane
reactors give promising technical and economical performance. The experimental results, obtained using Pd
membrane and reported in the literature, refer to
infinite selectivity of these membranes for hydrogen.
In this work we tried to make clear the discrepancy
which exists when comparing the theoretical results
from a model based on ideal membrane and experimental results which can be reached by the Pd membrane
characterized by some defects. The fact these defects
grow with time can also have effects on the agreement
between the experimental results and the model predictions.
Experimental Apparatus
An experimental plant to study methane steam
reforming reaction in a catalytic membrane reactor was
realized. It consists of a CMR packed with catalyst
(about 7 g), analytical units, and control systems for
flows and temperature.
The CMR consists of two concentric pipes: the inner
one is the membrane, whereas the outer is a SS shell.
The sealing between these two parts is realized by
means of graphite O-rings. The reactants are supplied
to the inner tube where catalyst is packed. The commercial catalyst 30% Ni over alumina has been furnished by Hengelhard de Meern BV. In the annular
space, the sweep gas flows in parallel flow mode with
the reactant stream. Both retentate and permeate
streams are analyzed by means of a GC. Mass flow
controllers have been used to control the feed and sweep
gas flow rates. The heating system consists of a
temperature controller (PID) connected to a heating
tape that winds up the SS shell. Two thermocouples
were located at the feed side of the reactor at the
beginning of the catalyst bed and at the exit of the
reaction volume. Temperature oscillations (up to 10 C)
have been observed in the system. An average value
of the temperature has been considered in the elaboration of the data.

well applied to have uniform metal deposition on

relatively complex geometry. The ceramic support is
activated, e.g., by stannous and palladium chloride
(SnCl2 and PdCl2), to have the metallic layer formation
on the external surface of the ceramic support. The PdAg alloy is obtained by diffusion at high temperature.
The amount of each deposited metal is consistent with
the required alloys composition. An intermediate ceramic layer (having 0.1 m of average pore size) is
required, between the metallic film and support, if the
support average pore size is larger than 0.1 m.
Solvated Metal Atom Deposition (SMAD). Recently, a new technique to deposit a very thin film on a
commercial ceramic membrane has been suggested by
Capannelli et al. (1993): Pt vapor and mesitylene have
been co-condensed at 77 K in a glass reactor. The solid
matrix produced has been heated up to 233 K, yielding
a solution stable at low temperature which has been
filled in a commercial ceramic tube made of four layers
(three R-alumina layers of different of pore sizes, as
macroporous support, and a thin -alumina layer). The
same technique has been used to deposit a thin layer of
Pd on the same type of ceramic tube; in this case Pd
vapor, mesitylene, and hexene-1 have been co-condensed
at 77 K in a glass reactor. This technique allows one
to deposit the metallic film (about 0.1 m) on the inner
surface of the ceramic support.
Mathematical Model
For membrane reactors, besides species generation
and axial fluxes (Ni), permeation fluxes through the
membrane have been considered in the development of
a mathematical model for steady-state operations (Barbieri and Di Maio, 1997). The basic assumptions are
plug flow on reaction and permeation side, isothermal
and isobaric conditions; MSR and WGS kinetics are
described by means of the global reactions (1-3) based
on reaction rates (rj) proposed by Xu and Froment. The
set of equations written in terms of fluxes consists of
the following ordinary differential equations:

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.

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3371

Table 1. Selectivity of the Products with Respect to the
Methane for EP and SMAD Membranes, Measured
during Reaction Tests
SMAD
EP

Figure 1. Degree of methane conversion versus space velocity/

reference space velocity (S/S0). S0 ) 11 g of catalyst/162 SCCM of
feed, T ) 500 C, H2O/CH4 ) 3, Pr ) 103 kPa, Pp ) 101 kPa, Qp
) 40 SCCM. Membrane thickness ) 20 m. (a) Degree of conversion of the membrane reactor, when the amount of catalyst is
reduced from the initial value of 11 g at a fixed feed flow rate of
162 SCCM. (b) Obtained for membrane reactor by increasing the
feed flow rate from the initial value of 162 SCCM at a fixed catalyst
amount of 11 g. (c) Calculated results obtained for a traditional
reactor with a change (one at time) in the amount of catalyst and
flow rate. The solid square represents the equilibrium value.

The driving force for hydrogen permeation is the

difference of the square root of the partial hydrogen
pressures between the reaction and permeate sides.
Simulation results showed that the counterflow configuration is not always better than the parallel one.
Depending on operating conditions (e.g., temperature,
pressure, feed and sweep flow rate, etc.), the conversion
degree for parallel flow is higher than that obtained by
means of the counterflow. The model shows that the
space velocity cannot be considered a design variable
due to the complex interaction between flow rate and
permeation through the membrane.
In traditional reactor models, if space velocity (S) is
changed by increasing (or reducing) the reactant flow
rate or decreasing (or increasing) catalyst weight, the
same results are obtained.
The model (Barbieri and Di Maio, 1997) shows (Figure
1) that a different conversion can be achieved with the
same (S/S0) value for the membrane reactor. It can be
observed that methane conversion is always higher than
that of the traditional reactor and that the difference
in the values depends on the way the S/S0 ratio is
changed. If the variation is imposed by increasing the
reactant flow rate, curve b is obtained. Instead, if the
variation is made by reducing catalyst weight, the
results obtained (curve a) show a significant difference
with respect to those of the traditional reactor.
Results and Discussion
In all experiments the analysis of the relative concentrations of the exit streams was made by measurement with a GC system. The conversion values have
been based on both shell and tube concentrations. The
experimental results clearly put in evidence the nonideal behavior of the Pd membranes utilized; its selectivity, moreover, is reduced with the progress of experimental runs. During the reaction tests, together with
the H2, a certain percentage of the reagents and
products were also permeated. This kind of phenomenon will be considered in the analysis of the experi-

H2/CH4

CO/CH4

CO2/CH4

2.61
0.87

3.07
1.85

1.79
0.58

Figure 2. Degree of methane conversion versus feed flow rate.

Experimental data for SMAD (solid circles) and EP (solid diamonds) membranes; fitting of experimental data (a) and model
results (b). The solid square represents the equilibrium value. T
) 536 C, H2O/CH4 ) 2.5, Pr ) Pp ) 101 kPa, and Qp ) 53.2
SCCM.

ments and in the comparison with the analytical

prediction. In Table 1 experimental selectivities are
reported. These selectivities have been calculated on
the basis of the GC analysis of the relative concentrations of the permeate and retentate streams.
The presence of all species in the permeate stream
indicates the nonideality of the membrane due to
pinholes and cracks on the metal layers. The two
membranes show different values of selectivities; in
particular, the SMAD membrane presents higher selectivities with respect to the EP one. The difference
in selectivity values can be explained assuming that two
transport mechanisms, in addition to the hydrogen
diffusion in palladium bulk, occur: Knudsen and surface
diffusion.
Being that the oxygenated species preferentially
adsorbed on the membrane surface (Xu and Froment,
1989a), both the SMAD and the EP membrane present
a H2/CH4 selectivity lower than the CO/CH4 and CO2/
CH4 selectivities.
In addition, in the EP membrane the Pd-Ag layer
(10 m) is located on the external surface of the support
and is thus far from the reaction region; here the
gaseous phase containing more reaction products than
the reaction zone could react (Capannelli et al., 1996).
So, CO and CO2 could react with H2 in the Pd layer to
give CH4 and H2O. These reactions do not occur for the
SMAD membrane, since the very thin Pd layer is
deposited on the internal surface of the support. In this
way it is possible to justify the lower selectivities for
the EP membrane with respect to the SMAD one.
Figure 2 reports the degree of methane conversion
against the reactant feed flow rate for a H2O/CH4 molar
feed ratio equal to 2.5. Solid circles in Figure 2
represent the experimental data obtained with the
SMAD membrane, while the solid diamonds represent
the experimental data for the EP membrane.

3372 Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997

Figure 3. Degree of methane conversion versus feed flow rate

for the EP membrane at two different feed molar ratios. Experimental data: (a; solid diamonds) m ) 2.5; (b; solid circles) m )
1.18. Model results: (c) m ) 2.5; (d) m ) 1.18. T ) 536 C, Pr ) Pp
) 101 kPa, and Qp ) 53.2 SCCM. The solid square represents the
equilibrium value at m ) 1.18, and the open square represents
the equilibrium value at m ) 2.5.

Figure 4. Degree of methane conversion versus feed molar ratio;

(solid circle) obtained with the SMAD membrane; (solid diamonds)
relative to the EP membrane; (dashed line) model results; (solid
line) equilibrium values. T ) 536 C, Pr ) Pp ) 101 kPa, Qr )
88.5 SCCM, and Qp ) 53.2 SCCM.

The degree of conversion decreases, increasing the

feed flow rate as shown by fitting (curve a) because of
the reduced time factor. This is in agreement with the
model (curve b), that predicts another small decrease
due to the reduction of residence time. It can be noted
that the two membranes show the same trend and that
the methane conversion values are very close to each
other. However, the EP membrane presents lower
conversion values with respect to the SMAD one due to
its lower selectivity.
In Figure 3 the experimental degree of conversion
against the feed flow rate for two feed molar ratios is
reported. The membrane used is the EP one. The data
obtained with a feed molar ratio equal to 2.5 (curve a)
showed the same trend as those obtained at H2O/CH4
) 1.18 (curve b). The conversion values obtained by
increasing the feed molar ratio are, of course, higher.
Figure 4 shows the degree of methane conversion
versus the feed molar ratio. Experimental data, performed with the EP membrane, show the same trend

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.

Figure 6. Experimental degree of methane conversion versus Qr

for the SMAD membrane. T ) 536 C, Qp ) 53.2 SCCM, m ) 4,
and Pr ) Pp ) 101 kPa. The solid square represents the equilibrium value.

as predicted by the model. On the same figure a point

referring to the SMAD membrane is also reported.
The effect of temperature on the degree of methane
conversion is shown in Figure 5. The conversion
increases, as predicted by the model, with the temperature. The agreement between experiments and the
model is good in the low-temperature range, but at
higher temperature values a significant difference is
observed.
Figure 6 reports the degree of methane conversion
against the reactant feed flow rate for a H2O/CH4 molar
feed ratio equal to 4. The membrane used is the SMAD
one.
The results reported in Figures 2-5 have been
compared to the theoretical predictions derived by the
model (Barbieri and Di Maio, 1967). The observed
discrepancy between the theoretical and the experimental data can be explained as follows. In the simulation
program only hydrogen permeates through the membrane, whereas the two membranes used were found to
be selectively permeable to all species. Particularly, the

Ind. Eng. Chem. Res., Vol. 36, No. 8, 1997 3373

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.

SMAD membranes showed a higher selectivity for

products than for reactants (see Table 1); thus, the shift
of equilibrium in the experimental cases has been higher
than that in the theoretical one, with subsequent
increase in conversion. The increase in conversion has
to be also related, for both membranes, to a dilution
effect due to the presence of the sweep gas in the
reaction side. In Figure 7 the experimental degree of
methane conversion as a function of Qr is compared with
the model predictions for different values of sweep gas
flow rates. The same values obtained in the experimental runs might also be achieved theoretically for a
sweep gas flow rate on the order of 500 SCCM. The
discrepancy observed might be the results of a combination of more effects: the higher presence of products in
the permeate stream, a certain increasing of sweep flow
rate (due to the permeation of all species), and the
presence of sweep gas in the reaction side.
Conclusions
The data presented in this work confirm the interest
of catalytic membrane reactors in methane steam
reforming reaction in terms of a possible increase of
conversion and the possibility of operating at mild
operating conditions. However, the fact that most of
the available Pd membranes will not behave as ideal
ones has to be considered. The existing models, in
general, assumed infinite selectivities for hydrogen. The
experimental results obtained in our work have shown
that also with noninfinite selectivities of membrane, if
appropriate operating conditions are introduced, interesting benefits can be obtained. For example, an
increase of the conversion value on the order of 20%,
with respect to the equilibrium one, has been observed
for H2O/CH4 equal to 2. However, the possibility of
operating at lower temperatures than those used in
traditional systems appears to be promising.
The experimental results show also that the two
different techniques used for the preparation do not
change the overall performance of the system, inducing
a good reproducibility in the obtained data. Nevertheless, the SMAD membrane gave certain higher conversion values than the EP one.

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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Received for review January 10, 1997

Revised manuscript received May 19, 1997
Accepted May 20, 1997X
IE970033W
Abstract published in Advance ACS Abstracts, July 1,
1997.
X