Separation and Purification Technology 72 (2010) 92–97

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Separation and Purification Technology

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

On the assembling of Pd/ceramic composite membranes

for hydrogen separation
Weidong Chen, Xiaojuan Hu, Rongxia Wang, Yan Huang ∗
State Key Laboratory of Materials-oriented Chemical Engineering, College of Chemistry and Chemical Engineering,
Nanjing University of Technology, Xin-Mo-Fan Road 5, Nanjing 210009, PR China

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

Article history: Composite palladium membranes are particularly useful in hydrogen separation because of their per-
Received 22 October 2009 fect permeability and permselectivity toward hydrogen, and porous ceramics are their most common
Received in revised form 18 January 2010 substrate materials. High working temperatures favor membrane output, but create difficulties with
Accepted 18 January 2010
membrane sealing and assembling. This work suggests a kind of facile and effective connector with
graphite as the sealing material. The connector is resistant to temperature cycling, and the leakage kinet-
Keywords:
ics was discussed. The possible graphite hydrogenation and the consequent membrane contamination
Composite palladium membrane
at high temperature were also investigated.
Porous ceramics
Graphite © 2010 Elsevier B.V. All rights reserved.
Sealing
Hydrogen separation

1. Introduction kets [8–11]. Apparently this is impractical for industrial application

The increase in hydrogen energy applications has greatly stim-
ulated the demand for small-scale hydrogen production and
compact hydrogen separators. Palladium (including palladium
alloy) membranes are particularly attractive because of their excel-
lent permeability and permselectivity toward hydrogen [1]. In
addition, there is also an increasing interest in the use of palla-
dium membranes as reactors that not only integrate the hydrogen
production and separation but also overcome the reaction ther-
modynamic constraints [2–4]. In order to improve the membrane
permeability and completely avoid the hydrogen embrittlement
problem, palladium membranes should be operated at high tem-
peratures.
To ensure the mechanical strength, conventional free-standing
palladium membranes are relatively thick, which decreases the
membrane permeance and increases the palladium cost. An ideal
solution is to support a thin layer of palladium or palladium alloy
on a porous substrate. Porous ceramics are the most common sub-
strate material, owing to their excellent chemical stability [5–7].
However, ceramics are brittle, making the membrane sealing and
assembling difficult at high working temperatures. One solution is
to glaze the end(s) of the porous ceramic tube so that the end(s) of
the membrane tube can be cooled down and sealed with rubber gas-
∗ Corresponding author. Tel.: +86 25 83172253; fax: +86 25 83172253.
E-mail address: huangy@njut.edu.cn (Y. Huang).
because of the heat loss and added volume to the membrane sep-
arator. In addition, the junction between the porous ceramics and
the glaze often causes membrane defects during the membrane
preparation and future operation. Binding the ceramic tube with
metals, e.g., by soldering or with an inorganic adhesive, is another
possibility, but this is difficult and requires special technology. Due
to the problems associated with porous ceramic substrates, porous
stainless steel (PSS) has received much attention as an alternative.
However, its pore size is often too big for membrane preparation,
and intermetallic diffusion may occur between PSS and the metal
membrane once in direct contact. As a consequence, it is neces-
sary to have a ceramic barrier between them [12,13]. Even though
the thermal expansion coefficient of the PSS is close to that of the
metal membrane, this cannot be regarded as an advantage of the
PSS because the ceramic barrier means that the membrane is not
directly supported on the PSS.
Graphite has also been used to seal composite membranes that
have ceramic substrates, for example by applying graphite gaskets
onto the faces of the two ends of the membrane tube [6,14]. How-
ever, this kind of sealing is poorly gas-tight, and the membrane
can be easily broken by over-pressurization. It would be ideal if
the membrane, like the metal tube, can be conveniently sealed
with connectors [15–17]. However, the key to the design of the
connector is to account for and limit the pressing force, and any
damage to the thin membrane layer must be absolutely avoided
during operation.
In this work, we introduced a kind of facile and effective
connector for membrane sealing, studied its resistance against tem-

1383-5866/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.01.010
 W. Chen et al. / Separation and Purification Technology 72 (2010) 92–97
perature cycling, and analyzed the leakage kinetics. The possible
contamination to the membrane by graphite under hydrogen at
high temperature was also investigated.
2. Experimental
The membrane substrate was an asymmetric porous Al2 O3 (o.d.,
12.5 mm; i.d., 7.6 mm; mean pore size measured by capillary flow
method, 0.2 ␮m; manufacturer, Jiusi Co., Nanjing, China), which
had a fine-porous layer on the shell side. All the membranes in this
work were prepared via electroless plating at room temperature.
Before plating, the substrate surface was activated using a conven-
tional SnCl2 /PdCl2 method [18]. The plating bath was composed of
PdCl2 (5 g L−1 ), Na2 EDTA (70 g L−1 ) and NH3 ·H2 O (28%, 250 mL L−1 ),
and the reducing agent was a 0.2 mol L−1 hydrazine solution. After
plating, the membranes were thoroughly cleaned with deionized
water at 333–363 K, and then with anhydrous ethanol before being
dried overnight at 393 K.
The membrane permeation tests were performed using the
H2 /N2 single gas method [6,12,13], and the pressure of the per-
meate side was always ambient. Before testing, the membrane was
firstly heated under nitrogen at 2 K min−1 up to 673 K, and this tem-
perature was maintained for 2 h under synthetic air (N2 :O2 = 4:1)
to burn organic remnants in the membrane.
Fig. 1. Typical Pd/Al2 O3 membrane prepared by electroless plating: (a) porous Al2 O3 substrate and palladium membrane; (b) substrate surface; (c) membrane surface; (d)
metallographic view of the membrane cross-section.
93
3. Results and discussion
A porous ceramic substrate and a typical palladium membrane
prepared by electroless plating are shown in Fig. 1. The palladium
layer looked uniform and lustrous, and adhered firmly to the sub-
strate surface.
3.1. The strategy for membrane sealing
To seal a palladium membrane safely and conveniently, the key
is to design a suitable connector that can be applied directly onto
the membrane surface. Difficulties include: the very thin palladium
layer can be easily broken by scratching, and the brittle ceramic
substrate limits the applied force that is necessary for gas-tightness.
Here, we suggest a kind of facile and effective connector, which is
depicted in Fig. 2, and the particular stratagems are: (i) increasing
the interface area between the membrane and the graphite gasket;
(ii) allowing the force created by screw tightening to be effectively
transferred into the interaction force between the membrane and
the gasket; (iii) greatly reducing the scratching on the membrane
during the screw tightening. In this design, the graphite gaskets
(or O-rings) with a trapezoidal section were used, which were fab-
ricated with a mold. Before use, they were annealed at 873 K for
2 h.
94 W. Chen et al. / Separation and Purification Technology 72 (2010) 92–97
Fig. 2. Schematic and photo of the suggested connector for composite palladium
membrane.
For laboratory use, we fabricated a very compact membrane
module with the suggested connectors. Its schematic and photo
are shown in Fig. 3, and an above-mentioned graphite gasket is
also demonstrated. The active length of membrane for hydrogen
permeation is 5 cm. To be on the safe side, we measured the ther-
mal expansion of the membrane substrate (porous Al2 O3 ) and
membrane module materials (SS-316L) with a dilatometer (Net-
zsch DIL 402C) at a heating rate of 5 K min−1 , and the results are
shown in Fig. 4. Their average thermal expansion coefficients at
473–873 K are 7.6 × 10−6 and 19.1 × 10−6 K−1 , respectively, which
are close to those reported in the literature [19,20]. Because of the
thermal-expansion-coefficient mismatching between the metal
and ceramic, such a membrane module concept is only applicable
for short membranes.
3.2. Resistance to temperature cycling
To study the effect and stability of sealing, a stainless steel tube
instead of real palladium membrane was firstly assembled into the
compact module (cf. Fig. 3) for leakage tests, so that the possible
interference caused by the leakages through membrane pinholes
Fig. 3. Schematic (above) and photo (below) of the small-scale membrane module
fabricated for laboratory tests.
Fig. 4. Thermal expansion rates of the porous Al2 O3 and stainless steel 316L as a
function of temperature.
can be avoided. Each temperature cycling includes a heating ramp
of 2 K min−1 , a temperature maintenance at 773 K for 0.5 h, and a
natural cooling down to room temperature. To test the sealing effect
each time, nitrogen was fed to the shell side of the stainless steel
tube, and the nitrogen leakage LN2 at the connectors was measured
with a bubble flow meter. The results are shown in Fig. 5. In general,
LN2 is always in an extremely low level. For example, it was never
larger than 0.4 mL min−1 at a pressure up to 50 bar, indicating the
connectors are highly gas-tight.
It can also be observed in Fig. 5 that LN2 is always linearly pro-
portional to the pressure. Therefore, the nitrogen leakage through
the connectors was supposed to mainly follow Knudsen diffusion
mechanism. When the temperature was increased to 773 K for the
first time, a significant increase in LN2 occurred (compare between
Fig. 5. Nitrogen leakage through the connectors as a function of pressure during
temperature cycling (the arrow shows the sequence).
 W. Chen et al. / Separation and Purification Technology 72 (2010) 92–97
Fig. 6. Hydrogen and nitrogen fluxes through a palladium membrane under 2 bar.
curves “” and “”), and the possible cause is the appearance of new
pores inside of the graphite gaskets or between them and the mem-
brane during the first heat treatment. Afterwards, the influence
of the temperature on LN2 became highly reversible. Surprisingly,
Fig. 5 reveals that the LN2 rates at 773 K are very close to corre-
sponding those at room temperature despite of such a huge change
in temperature. According to Knudsen diffusion mechanism,
LN2 ∝ T −0.5 (1)
Apparently, the actual correlation between LN2 and T did not obey
this principle. Probably, some new pores or an increase in pore
size reversibly occurred at high temperature. Note that Eq. (1) is
based on the assumption that the size and number of the pores are
constant.
Fig. 7. Schematics of the Pd/Al2 O3 membrane with glazed ends and the membrane
testing cell.
95
Fig. 8. The palladium membrane before (above) and after (below) graphite coating.
A Pd/Al2 O3 membrane (palladium thickness, 5 ␮m) was assem-
bled and tested at 723 and 773 K, and the fluxes of hydrogen
and nitrogen (denoted as JH2 and JN2 ) are presented in Fig. 6. The
increase in temperature led to an increase in JH2 , and JH2 was con-
stant with time-on-stream. Note that a dense palladium membrane
will be exclusively permeable for hydrogen, and allow no other gas
(such as N2 ) to pass through. However in practice, an ultra-thin pal-
ladium membrane is very difficult to be completely pinhole-free,
and consequently:

JN2 = LN2 + JN (2)
2
 is the nitrogen leakage through the membrane pinholes.
where JN
2
Fig. 6 shows that the measured JN2 is 1–2 mL min−1 . According
to our experience over similar palladium membranes, JN2 should be
very close to JN  , i.e. L
N2 is most likely negligible. Even if LN2 = JN2 ,
2
it will be still negligible against JH2 . In commercial applications, the
membrane size will be much larger than that in this test. However,
each membrane tube, no matter how long it is, will only have two
ends to be connected, and LN2 vs. JH2 will be further lower. In con-
clusion, the sealing of the palladium membrane by the suggested
connectors is highly feasible.
3.3. Interactions between graphite and palladium membrane
In general, the permeation of hydrogen through a dense pal-
ladium membrane follows a solution-diffusion mechanism [1],
Fig. 9. Permeation performance of a palladium membrane at 623 K before and after
graphite coating.
96 W. Chen et al. / Separation and Purification Technology 72 (2010) 92–97
Fig. 10. Permeation performance of the palladium membrane after graphite coating. Left: hydrogen flux as a function of pressure; right: kinetic analysis according to Sievert’s
Law.
which includes five steps: (i) hydrogen molecules are chemisorbed
on the palladium surface and dissociated into hydrogen atoms;
(ii) hydrogen atoms are dissolved into palladium layer, forming
a PdHx alloy; (iii) hydrogen atoms diffuse from one side to the
other; (iv) hydrogen atoms escape from the membrane but remain
chemisorbed on the palladium surface; (v) hydrogen atoms recom-
bine into molecules and get desorbed. In most cases, Step (iii)
is rate-determining, and the permeation kinetics follow Sievert’s
Law:
0.5
JH2 = F(PRet 0.5
− PPerm )
where F is the hydrogen permeance, PRet and PPerm are the hydrogen
pressures at the retentate and permeate sides.
Palladium is a universal catalyst for numerous hydrogenation
reactions [21–23]. When graphite is used as the sealing material,
hydrogen will permeate through the membrane and meet with
the graphite rightly on the surface of the palladium. Once the
hydrogenation of graphite is gradually catalyzed by palladium, the
long-term sealing effect might be a problem, and it is even worse
if the hydrogenation products lead to a coking on the membrane
surface. It was well known that coking severely decreases the mem-
brane permeability [24,25].
In order to study the interaction between graphite and the pal-
ladium membrane, we deposited some graphite on the membrane
surface and tested its permeation behaviors. A partially glazed pal-
ladium membrane and the testing cell (as depicted in Fig. 7) were
used in this test. For reference, the permeability of the fresh mem-
brane at 673 K was firstly measured. The graphite coating was
carried out by applying some graphite powder onto the membrane
surface and slightly polishing with a finger. (Before use, the graphite
powder had been preheated at 873 K for 2 h in air.) As can be seen
in Fig. 8, the membrane was significantly changed in color and
exhibited characteristic luster of graphite after coating.
Fig. 9 illustrates the effect of graphite on membrane perfor-
mance. Little change can be observed in membrane permeability,
indicating that the suspected graphite contamination to the palla-
dium membrane did not exist. (One should keep in mind, however,
that a decrease in the membrane permeability cannot be ruled out
once the graphite loading is high enough to make a significant
physical blockage.)
To further verify the non-contamination of the graphite, the
membrane with graphite coating was tested at different tem-
peratures, and the results are shown in Fig. 10. The increasing
temperature steadily increases the hydrogen flux, giving an
apparent activation energy of 14.7 kJ mol−1 , and the membrane
permeation behavior can be described perfectly by Eq. (3). These
results are typical features for the palladium membrane [1].
4. Conclusion
This work suggests a kind of facile and effective connector for
sealing and connection of the composite palladium membranes
with graphite as the sealing material. The connector is resistant
to temperature cycling, and the leakage kinetics was discussed.
(3) The possible graphite hydrogenation or the consequent membrane
contamination at high temperature was also investigated.
Acknowledgments
The authors are sincerely thankful to the financial support by the
Natural Science Foundation of China (20576055 and 20876075), the
National High-Tech R&D Program of China (2009AA05Z103) and
the Natural Science Foundation of the Higher Education Institutions
of Jiangsu Province, China (09KJA530003). A special thank goes to
Prof. Y. Fan, Membrane Science and Technology Research Center,
Nanjing University of Technology, for providing the porous ceramic
materials.
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