Journal of Membrane Science 368 (2011) 264274

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Experimental tests on steam reforming of natural gas in

a reformer and membrane modules (RMM) plant
M. De Falco a, , G. Iaquaniello b , A. Salladini c
a
Faculty of Engineering, University Campus Bio-Medico of Rome, Via Alvaro del Portillo 21, 00148 Rome, Italy
b
Tecnimont KT S.p.A., Viale Castello della Magliana 75, 00148 Rome, Italy
c
Processi Innovativi, Corso Federico II, 67100 LAquila, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A reformer and membrane modules (RMM) test plant with a hydrogen capacity of 20 Nm3 /h has been
Received 4 September 2010 designed and built to investigate the performance of said innovative architecture at an industrial level.
Received in revised form 28 October 2010 A major benet of the proposed RMM conguration is the shift in the chemical equilibrium of the steam
Accepted 19 November 2010
reforming reactions by removing the hydrogen produced at high temperatures, thanks to the integration
Available online 25 November 2010
of highly selective Pd-based membranes. In this way, the process can operate at a lower thermal level
(below 650 C in comparison to the 850950 C temperature needed in traditional plants).
Keywords:
Four types of Pd-based membranes, three already installed and one yet to be assembled, with an
Hydrogen production
Selective membrane
active area in the range 0.120.4 m2 , are tested in order to compare performance in terms of permeated
Steam reforming hydrogen ux. Moreover, a noble metal catalyst supported on a SiC foam catalyst is placed inside the
Catalyst foam reactor in order to improve thermal transport inside the reforming tubes.
Firstly, this paper introduces the plant design criteria: the process scheme, the construction engineer-
ing of reformers and membrane units and the control system implemented to maximize experimental
outputs. The main experimental tests results are then reported and discussed, at least in a preliminary
manner. About 1000 operating hours and more than 70 heating and cooling cycles were performed. The
average H2 permeability for membranes tested are calculated and compared, and permeability expres-
sions are reported. An overall feed conversion of 57.3% was achieved at 600 C, about 26% higher than
what can be achieved in a conventional reformer at the same temperature, thanks to the integration of
selective membranes.
The 20 Nm3 /h RMM installation makes it possible to completely understand the potential of selec-
tive membrane application in industrial high-temperature chemical processes, and represents a unique
installation worldwide.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Natural gas (NG) steam reforming is the main hydrogen produc-
tion method. Nowadays, 48% about of 500 109 Nm3 of hydrogen
produced each year worldwide is obtained from this process [1].
The main reactions involved in NG steam reforming are
endothermic and controlled by chemical equilibrium, achieving
signicant hydrogen yields at high temperatures only (850900 C).
As a consequence, a part of methane feedstock has to be burned in
furnaces, reducing the overall efciency of the process, increasing
greenhouse gas (GHG) emissions and the dependency of hydrogen
cost on natural gas cost.
Corresponding author. Tel.: +39 3476809041.
E-mail address: m.defalco@unicampus.it (M. De Falco).
In recent years, R&D centres and industries have focused their
efforts on the development of technologies to reduce the process
temperature. The integration of hydrogen-selective membranes
seems to be the most promising way to enhance hydrogen yield
at lower temperatures (450650 C), since the selective removal
of hydrogen produced in the reaction zone makes it possible to
keep the gas mixture composition removed from the balanced com-
position, so that equilibrium conditions are not achieved and the
endothermic reactions are supported at a lower temperature.
Pd-based supported membranes seem to be the most promising
membrane type, thanks to the high selectivity and good permeation
ux [210]. They can be integrated in the steam reforming pro-
cess in two congurations: directly inside the reaction environment
so that the hydrogen produced by the reactions is immediately
removed (Membrane reactor, MR conguration) [1117]; or assem-
bled in separation modules applied downstream to reaction units
(Reformer and membrane module, RMM conguration) [18,19].

0376-7388/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.11.050
 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274
Fig. 1. Process scheme of prototypal plant.
In previous works, the authors have assessed and compared the
benets and drawbacks of both congurations [20,21]. The main
ndings were as follows:
the Pd-based are used at a temperature below 500 C in order to
avoid possible damages due to stability problems, as suggested
by [22]. This limits the reaction operating temperature in MR. In
the RMM conguration the operating temperatures in the reactor
and in the separator are de-coupled and may be set separately;
hydrogen production costs for the RMM technology are more
than 10% lower than those of the conventional H2 scheme.
On the basis of these ndings, an innovative 20 Nm3 /h proto-
typal RMM plant was designed and built by Tecnimont-KT in
Chieti (Italy). The plant comprises two-step reformers, working at
550650 C, and two membrane modules at 450 C, as described
in the following paragraphs. This installation, the rst of this type
and size, makes it possible to completely understand the potential
of selective membrane application in industrial high-temperature
chemical processes. This paper reports experimental data collected
during the testing phase, allowing for better comprehension of the
RMM plants behaviour within the range of operating parameters
tested.
2. Process scheme
The plant scheme is shown in Fig. 1 and consists of two-step
reformer and membrane modules.
265
Natural gas from battery limits or from cylinders at 20 barg is fed
through the pressure regulator and ow controller to the desul-
phurisation (DS) reactor in order for sulphur compounds to be
removed. Sulphur content in the desulphuration outlet stream has
to be maintained at values <0.1 PPM, since sulphur is known to be
extremely detrimental to both palladium alloy membranes and cat-
alysts. The desulphurised feed is mixed with steam and preheated
in the convection section. It then enters the rst reforming stage
where reactions take place at 550680 C. The reformed gas prod-
uct is cooled down at 450 C and enters the rst separation module,
where a retentate, recycled from the second reformer stage, and a
mixture of H2 plus sweeping steam are produced. After the sec-
ond reformer stage at 650 C, the output mixture is cooled from
650 C to 450 C and routed to the second separation module. H2
from both modules are mixed together and sent for nal cooling
and condensate separation. Retentate from the second stage is sent
to the are.
The operating pressures of membrane units for both the shell
and permeate sides are controlled using a back pressure regula-
tor, and both membrane modules are protected using a pressure
relief regulator installed on the income lines. All the vent points
are connected to the main vent system and routed to the are.
In two-step reforming, the reaction heat is provided by two
independent hot gas generators in order to set the reforming tem-
peratures as required by the tests.
Fig. 2 shows some images of the industrial test plant which
occupies an area of 1000 m2 .
The plant is equipped with a complete control system in order
to monitor the main operating parameters, i.e.:
266 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274

Fig. 2. Views of industrial test plant.

mass ow for natural gas, reactant steam, sweeping steam to the
membrane separator and hydrogen produced;
temperatures and pressures before and after each reformer and
separation step;
Pressure drop across the catalytic tube;
CH4 , CO and CO2 concentrations monitored by an ABB
URA14online infra-red NDIR multiple analyser, at the outlet of
the two reforming steps and of the membrane modules;
H2 concentration, analysed by an ABB Caldas 17 thermal conduc-
tivity detector and through a PerkinElmer GC Autosystem XL.
By acting on the reformer outlet temperature and on the steam to
carbon ratio (R), it is possible to generate different syngas compo-
sitions to be fed to the separation module, and to analyse the role
played by partial pressures of the main components (CH4 , CO, CO2
and H2 ) in the separation performance.
 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274 267

Heating and cooling of the membrane are carried out in a nitro-

gen or nitrogensteam mixture atmosphere. Testing takes place in
continuous mode for 5 days. During the night, the plant operates at
low load, with methane and steam, while it is cooled by nitrogen
during the week-end before being stopped completely.

3. Reactor and separator design

3.1. The two-step reformer design

The reformer module consists of two main sections:

1. the radiant box, containing the catalytic tube charged with the
catalyst;
2. the convection section, where heat is recovered from the ue
gases for preheating and superheating feed and steam.

The steam is produced separately by a real hot oil boiler. The steam
reforming reactions as follows:
CH4 + H2 O CO + 3H2 , methane steam reforming (H 298K = 206 kJ/mol) (1)

CO + H2 O CO2 + H2 , water gas shift (H 298K = 41 kJ/mol) (2)
CH4 + 2H2 O CO2 + 4H2 , global reaction (H 298K = 165 kJ/mol) (3)
are carried out at temperatures in the 550650 C range and pres-
sure of up to 20 barg, while the ue gases coming from the hot
generator may reach a temperature in excess of 800 C. The radiant
chambers design is quite conventional: it differs only by the heated
Fig. 3. Catalyst supported on SiC foam for steam reforming process. length of the reformer tube (3 m), the tube metallurgy and the
contained catalyst. One of the advantages of the proposed architec-
Table 1 ture is that low-cost stainless steel is required for the catalyst tube
Overview of inlet mixture composition used in membrane testing. instead of expensive material such as centrifugally cast HP25/35
H2 (%vol.) CH4 (%vol.) CO2 (%vol.) CO(%vol.) H2 O(%vol.) chromium/nickel alloy, needed to resist at the high operating tem-
2430 69 69 12 5459
perature of traditional steam reforming tubular reactor, assuring at
the same time a good conductivity.
Traditionally, there is a strong endothermic reaction region
The syngas composition range used as feed in membrane testing located at the inlet of the catalytic tubes during the steam reform-
is reported in Table 1. Alternatively feed gas composition may also ing of natural gas. In such a section, the rate limiting process is the
be obtained by mixing up the pure components directly from the heat transfer from the combustion gases through the heated reactor
cylinders. wall and catalyst bed.
The inlet temperature to the separation modules can be modi- Since the reformer reactions are performed at lower temper-
ed in the 400500 C range by acting on the cooling media ow ature, how close the CH4 conversion is to the equilibrium value
of the pre-heater installed just before the module. On the perme- must be assessed. Preliminary experimental results [23] raised
ate side, steam is added as sweeping stream to lower the partial some doubts about the effectiveness of industrial, nickel-based cat-
pressure of hydrogen, increasing the driving force for separation. alysts supported on ceramic materials such as -Al2 O3 , MgO and

Fig. 4. Tube ECN membrane separator 13 (total surface 0.5 m2 ).

268 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274

MgAl2 O4 . A noble metal catalyst supported on a SiC foam catalyst,

shown in Fig. 3, is looked at in order to enhance conductive heat
transfer and catalyst activity. The catalyst is the SR-10, produced
by BASF and composed by RhPt on activated and stabilized Al2 O3 .
The support is a SiC cylinder shaped foam, 150 mm long and with
a diameter of 60 mm. The open cross ow SiC foam is expected to
increase effectiveness of the heat transfer through convection.
The use of a foam as a catalytic support will also result in a lower
pressure drop in the catalytic bed which in turn reduces the energy
costs associated with gas compression and with the recirculation
of gas streams as in the proposed architecture.

3.2. Dense Pd-based membranes for hydrogen separation

Four different membrane separators, able to work at high tem-

peratures, were planned for installation on the prototypal plant.
During the last decade, signicant efforts have been devoted
to developing thin lm (<10 m) Pd-based membranes supported
on different porous substrates, and to moving the technology from
lab scale to larger surface dimensions. Three of the few membrane
providers/developers ECN from the Netherlands [24], MRT from
Canada [25] and a company from Japan were selected and their
membranes assembled in the steam reforming plant. A fourth com-
pany, Acktar from Israel [26], is also involved, but its membrane
will be tested later. All membranes are Pd-based, but have differ-
ent supports: the membranes developed by ECN and the Japanese
manufacturer use a ceramic support, while Acktar and MRT mem-
branes use a stainless steel substrate. All the membranes are PdAg
alloy membranes, with the exception of ECNs which is a Pd mem-
brane. The membranes have a tubular geometry, with the exception
of MRTs which is planar. Table 2 reports the main properties and
geometry of membranes included in the project. Figs. 46 show the
Fig. 5. Tubular membrane separators (Japanese manufacturer).
modules assembled in the plant, while Fig. 7 depicts Acktars novel
stainless steel alumina membrane support.
The monitoring system makes it possible to retrieve a large
4. Results and comments amount of reliable information about methane conversion, gas
stream compositions, operating temperature and pressures. For
A wide range of operating conditions were tested to assess cor- example, Fig. 8 shows the average molar fraction, in steady-
rect operability of the RMM plant in an industrial environment and state condition, of the main components at the rst reforming
to have clear evidence of the technologys potential. steps outlet at a different steam-to-carbon ratio (R), pres-

Table 2
Main properties and geometry of the membranes.

Developer Substrate/support Membrane selective layer Thickness of the selective layer (m) Manufacturing method Geometry

ECN Alumina Pd 39 Electroless deposition Tubular

Condential Alumina Pd/Ag 23 Electroless deposition Tubular
MRT Stainless steel Pd/Ag 25 Proprietary Planar
Acktar Stainless steel + alumina Pd or Pd/Ag 35 Reactive sputter deposition Tubular

Fig. 6. MRT at membrane.

 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274 269

Fig. 7. Acktar novel stainless steel alumina membrane support.

sure of 10 barg, temperature of 600 C and gas mixture space
velocity (SV) of 5150 h1 . It has to be noticed, here and in
the gures reported below, that the composition of steam
reforming reactors outlet stream is always much close to the
equilibrium.
The performance of the low-temperature reformers and mem-
brane separation modules, the effect of feed ow on methane
conversion and the RMM plants global performance are reported
and assessed below.
4.1. Low temperature steam reformer performance
Several tests have been carried out by varying the reformer out-
let temperature from 550 to 680 C at 10 barg. Fig. 9 shows testing
results which show that methane conversion strongly increases
when the reforming temperature is higher (32% at 550 C, 64%
at 680 C). This is due to thermodynamics, considering the strong
endothermicity of the steam reforming reaction (1).
Fig. 10 reports methane and hydrogen contents at the rst
reformer outlet during steady-state operation at 600 C, steam-to-

Fig. 8. Average measurements of main components at the outlet of rst reforming step with different steam to carbon ratio (R) at 10 barg, 600 C and s.v. = 5150 h1 .
270 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274

Fig. 9. Methane conversion versus reforming temperature at 10 barg.

carbon ratio R of 4.8 and 10 barg after 960 h. It is worth noting that
no sign of deactivation has been detected yet after a fairly long
period of operation.
Fig. 11 shows methane conversion at various gaseous inlet
hourly velocity. The reactants conversion is affected by space
velocity (SV) in two ways:
1. increasing SV improves the heat and mass transfer mechanism,
supporting the reactions;
2. while increasing SV reduces the residence time, with a negative
effect on methane conversion.
that at low SV, the positive effect on heat and mass transfer domi-
nates, while at higher SV the negative effect becomes predominant.
The maximum methane conversion obtained at the set operating
conditions is equal to 49.5%.
4.2. Membrane permeability expression and separation unit
performance
Membrane permeability is assessed by using data regarding the
permeated hydrogen ux versus module temperature.
First of all, it is assumed that SievertsFicks law is valid for the
membranes tested, i.e.:

The gure clearly shows that methane conversion follows a non- Perm  0.5 
JH2 = pH ,up p0.5 (4)
monotonic prole, with a maximum of about 5000 h1 , meaning 2 H2 ,down

Fig. 10. Methane and hydrogen content in the dry product along 960 h operation.
 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274 271

Fig. 11. Methane conversion versus gaseous (inlet) hourly space velocity at an outlet temperature of 600 C, at a pressure of 10 barg and S/C of 4.8.

where JH2 is the permeated hydrogen ux, is the membrane thick-
ness and pH2 ,up and pH2 ,down are the hydrogen partial pressures up
and downstream.
Then, the inlet temperature of the membrane separation mod-
ules is varied within the 400450 C range. It is well-known that
hydrogen ux through the membrane usually increases with an
increase in temperature since, according to the Arrhenius law,
membrane permeability depends on operating temperature:
 E 
Perm = A exp
a
(5)
RT
where A and Ea are a pre-exponential factor and the apparent
activation energy, respectively. These two membrane param-
eters can be found by testing the plant using the following
procedure:
1. the hydrogen ux is measured at different operating tempera-
tures (400450 C) with a xed pressure difference between the
shell and lumen (10 barg in retentate, 0.4 barg in permeate zone);
2. assuming that permeability depends on temperature as per
Arrhenius law and the SievertsFicks law, the hydrogen ux

Fig. 12. Ln (permeance) vs. 1/T for the 3 Pd based membranes tested.
272 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274

Fig. 13. Hydrogen content in the retentate side of the separation module versus the operating temperature (MRT membrane).

Table 3
Permeabilities of the three Pd-based membranes tested.

Membrane A (kmol/(m h kPa0.5 )) Ea (kJ/mol) R2 Permeability expression Permeability at 450 C (kmol/(m h kPa0.5 ))

ECN 1.72 101 77 0.705 1.72 101 exp (77,000/RT) 4.67 107
MRT 5.75 104 35.3 0.611 5.75 104 exp (35,300/RT) 1.61 106
Condential 9.31 102 80.4 0.844 9.31 102 exp (80,400/RT) 1.44 107

is given through the following expression, called Richardson which can be linearised as follows:
equation:
C2
ln(Permeance) = C1 + (8)
A exp(Ea /RT ) T
JH2 = (p0.5 0.5
H2 ,up pH2 ,down ) (6)

where
Eq. (6) can also be written as: A
C1 = ln
JH2 A exp(Ea /RT ) (9)
= Permeance = (7) Ea
p0.5 p0.5 C2 =
H ,up2 H ,down
2 R

Fig. 14. Methane conversion for reformer and membrane module at various space velocities.
 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274 273

Fig. 15. CH4 content for integrated process (reactors pressure = 10 barg, temperature = 600 C, S/C = 4.8, ECN membrane module): reaction (R-01) H2 separation (M-01);
reaction (R-02) H2 separation (M-02).

3. the data collected are reported as ln (Permeance) vs. 1/T diagram.
If the data are arranged on a straight line, the SievertsFicks law
assumption and the permeability Arrhenius dependency on the
temperature are veried. Moreover the values of A and Ea can be
obtained from the slope and intercept of the tting straight line.
Fig. 12 reports experimental data for the three membranes tested
and the linear regression expressions. Table 3 reports the A and
Ea values obtained, the interpolation correlations (R2 ), the expres-
sion of permeability and the values at 450 C. It must be noted that
the MRT membrane allows the best performance at the operating
conditions tested.
Fig. 13 shows the variation of the hydrogen ux with the MRT
membrane modules operating temperature. By raising the tem-
perature from 400 C to 425 C, the retentate hydrogen content
is reduced from 58.5% to less than 56.2% vol., conrming the
improvement in the module performances due to the dependency
of permeability on module temperature (Eq. (5)).
4.4. The RMM plants global performance
Fig. 15 shows the global performance of the new architecture.
Methane conversion at the rst reformer (R-01) outlet is equal to
45.5% (corresponding to a methane concentration of 19.2%), while
at the second reformer outlet (R-02) it increased to 57.3% (methane
concentration of 15.5%) with the same outlet temperature and
steam-to-carbon ratio, giving the idea that the improvement is due
to membrane module integration. It is worth noting that the nal
conversion by the RMM plant is 26% greater than the maximum
conversion using the traditional process, with the same operating
conditions.
This value has been obtained by installing a membrane area in
the separation module placed between the two reformers equal to
0.4 m2 . If the area is increased, global methane conversion increases
as well thanks to the better separation performance of the mem-
brane module, as seen in Fig. 16 which shows the impact of such
parameter versus the feed conversion, calculated by means of a
process simulation software, SimSci Esscor PRO II, and assuming

4.3. Effect of feed ow on methane conversion

Feed ow is varied within 25110% of the design ow.

Fig. 14 reports methane conversions versus SV. Unlike the sin-
gle reformer behaviour, which shows a non-monotonic prole (see
Fig. 11), the RMM plant is negatively affected by SV since methane
conversion continuously decreases, with a value of 60% at 4290 h1
and 54% at 6870 h1 . As previously stated, increasing SV leads to an
improvement in the heat and mass transfer mechanism, support-
ing the reactions, but at the same time it reduces the gas mixtures
residence time with a negative effect on reactions and hydrogen
separation. This dual effect leads to a non-monotonic prole of
methane conversion in the reformers (Fig. 11), while in the sep-
aration modules, only the negative effect occurs and membrane
performance worsens. On the whole, the reduced hydrogen ux
through selective membranes leads to a worse plant performance,
Fig. 16. Effect of membrane area increasing on methane conversion, assembling
expressed in terms of lower nal methane conversion. ECN membrane modules.
274 M. De Falco et al. / Journal of Membrane Science 368 (2011) 264274
the installation of ECN membrane modules with a constant perme-
ance equal to that obtained at 430 C. By increasing the membrane
surface by a factor of two between R-01 and R-02, it is possible
to calculate an overall conversion of 62.8%, 38% greater than the
conversion obtained from a traditional plant.
The effect of selective membranes on the methane concentra-
tion in the retentate gas can be analyzed by looking at the difference
between the R-01 outlet (19.2%) and the rst separation module
outlet (24.2%). Said effect appears to be less signicant (from 15.5%
to 16%) in the second separation module, mainly due to the fact
that the second module surface was 1/5 of the rst (see Fig. 15).
5. Conclusions
An innovative 20 Nm3 /h prototypal RMM plant comprising two-
step reformers working at 550650 C and two membrane modules
at 450 C, has been designed and built by Tecnimont-KT in Chieti
(Italy). Four types of Pd-based membranes, three already installed
and one to be assembled, are compared in terms of permeated
hydrogen ux. Moreover, a noble metal catalyst supported on a
SiC foam catalyst is placed inside the reforming tubes in order to
enhance thermal transport inside the catalyst bed.
Preliminary experimental tests have conrmed the potential of
said technology: an overall feed conversion of approximately 57.3%
was achieved at 600 C, 26% higher than what can be achieved in
a conventional reformer at the same temperature thanks to the
integration of selective membranes.
Said conversion could be increased up to 62.8% by doubling the
membrane surface by a factor of two.
Moreover, the effect of operating temperature and gas mixture
space velocity has been evaluated over a period of 1000 h without
major variations in membrane behaviour.
The permeability expressions of the three membranes installed
in the plant have been calculated by interpolating experimental
data, showing a good performance in terms of the membrane mod-
ules hydrogen separation.
The prototypal RMM plant is the rst installation of this type
and size in the world and makes it possible to completely under-
stand the potential of selective membrane application in industrial
high-temperature chemical processes. Further experimental tests
are planned in the future to verify these conclusions and to better
understand membrane behaviour over a longer period of operation.
Acknowledgments
This work was carried as part of the project entitled Pure hydro-
gen from natural gas reforming up to total conversion obtained by
integrating chemical reaction and membrane separation, funded
by MIUR (FISR DM 17/12/2002) -Italy.
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