i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 0 1 3 6 e1 0 1 4 0

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Technical Communication

Simplified, plate-type Pd membrane module for hydrogen

purification

Kyung-Ran Hwang, Shin-Kun Ryi, Chun-Boo Lee, Sung-Wook Lee, Jong-Soo Park*
Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon 305 343, Republic of Korea

article info abstract

Article history: A simplified, plate-type membrane module for hydrogen separation has been designed. It
Received 14 March 2011 can be constructed without the need for a complicated bonding apparatus and tested
Received in revised form without any module chamber. A double o-ring sealing mechanism was applied for easier
19 April 2011 assembly and ensured module-sealing. The assembled membrane module has good
Accepted 20 April 2011 performance in a high-pressure test. The module is suitable for application as a compact
Available online 2 July 2011 hydrogen purification system due to its simple assembly.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Keywords: reserved.
Membrane module
Pd membrane
Hydrogen
Purification
Metal support

1. Introduction since only hydrogen is soluble in Pd and diffuses in a Pd-based

membrane. This has many advantages - design of compact
Hydrogen is an important gas for many chemical reactions reactors, lower capital costs, fewer moving parts and inte-
such as oil reforming, sulfur reduction from oil, purification of gration with chemical reactors for simultaneous chemical
metals, hydrogenation and reduction of fine-chemicals. It is reactions and hydrogen separation. For this reason, numerous
also used in many semiconductor processes as a carrier gas research papers have reported on the hydrogen membrane
[1]. Hydrogen has recently attracted worldwide attention due [2e5], hydrogen purification system [6,7], and a catalyst-
to its application in clean power generation systems. membrane system [8e14]. Herein, the membrane module is
Hydrogen is usually produced from reforming process of an indispensable part of the above-mentioned research fields.
hydrocarbon sources and then his separation steps. Hydrogen The assembly technique to join the membranes and modules
purification with pressure swing adsorption, cryogenic distil- is very important to achieve hydrogen purification and for
lation or membrane separation is an essential process to reaction/separation studies. Various methods have been
remove impure gases such as carbon dioxide and carbon employed to join metallic membranes with metallic modules;
monoxide. Purification using an alloy membrane of palladium thermal bonding methods such as arc welding [15,16], brazing
(Pd) is the best method to obtain ultra high-purity hydrogen with CueAg alloy fillers [16,17] and diffusion bonding

* Corresponding author. Tel.: þ82 42 860 3664; fax: þ82 42 860 3495.
E-mail address: deodor@kier.re.kr (J.-S. Park).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.04.146
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 0 1 3 6 e1 0 1 4 0 10137

[16,18e20] and physical methods such as tightening with bolts mold using a homemade press. The compressed nickel support
and nuts [21,22]. It is well known, however, that the welding was treated at 900  C under H2 for 2 h to improve its mechanical
and brazing methods are not acceptable since the high strength, and polished to reduce its surface roughness. The
temperature and metal fillers required for the bonding cause polishing process consisted of manual (silicon carbide paper,
serious damage to the membrane film and its performance 10 min) and automatic (alumina slurry with 0.9 mm, 10 min)
[16,17]. Li et al. [23] devised a novel configuration to prevent polishing steps. The polished support was washed several
the destruction of the Pd film from the welding and to address times by de-ionized water and dried under a vacuum at 60  C.
issues related to modularization and scale-up of the Pd The degree of surface polishing was identified with a vacuum
composite membrane. They have welded the porous stainless leak test. The vacuum in a tester equipped with the raw nickel
steel support with a solid stainless steel wafer before support was instantly destroyed, while in case of the polished
a substrate modification and Pd film deposition, resulting in support, the vacuum leak rate was 5 mm Hg/min.
good performance. Diffusion bonding has recently been used The DC/RF power magnetron sputtering system with
in membrane module assembly due to no heat-affected zones a plasma cleaning system was used to coat the Pd-based
and no need for bonding materials different from the welding membrane film over the prepared metal support. Firstly,
and blazing methods. The defect-free PdeAg rolled alumina, as an inter-diffusion barrier between Pd and Ni
membranes 50 mm thick have been produced by means of metals, was coated on it at 400  C during 6 min with the
a diffusion bonding procedure based on the high mobility of rotation of a sample holder and then Pd was coated on a thin
silver atoms [16]. The joining procedure consists of a thermal alumina layer for 60 min at 400  C, also with the rotation of the
treatment at 1100  C for 1 h under controlled atmosphere and sample holder. After that, Cu was coated on the Pd layer for
a compression step. We assembled a plate-and-flame type 30 min at room temperature, once again with rotation. After
membrane module consisting of a unit cell and a housing by the PdeCu deposition, the Cu reflow was performed at 650  C
means of low temperature (500  C) diffusion bonding of for 2 h. The surface images of the prepared metal support and
membranes with a nickel metallic module and silver foils [18]. membrane were obtained by scanning electron microscopy
However, the complicated apparatus comprising a pair of (FE-SEM, HITACHIS-4700).
covers, a pair of membranes, a pair of porous alumina as
a support, a pair of ring-shaped silver foils and a membrane 2.2. Design of membrane module
module unit cell body and thermally bonded process are
needed for diffusion bonding. Moreover, the assembled The plate-type membrane module was designed to be used for
module should be installed into a housing to prevent the hydrogen purification without any housing or module
membrane film becoming damaged by air contact during chamber. The membrane module consists of the following
operations. Xie et al. [21] designed plate-type PdeAg parts: flanges, metal o-rings and plate-type membrane. These
membrane modules consisting of a membrane foil, porous parts were tightened together with bolts and nuts through the
stainless steel substrate, test frame and flange and tightened holes on the edges of the flanges. Two metal o-rings were used
together with bolts and nuts instead of thermal bonding for sealing the module.
methods. They observed that the inter-metallic diffusion
between the membrane foil and the substrate and pre- 2.3. Permeance test in a membrane module
treatment of the substrate with polishing and etching nega-
tively affected the hydrogen permeation flux. In our previous An experimental schematic diagram for the permeation test
report [22], a plate-and-flame type hydrogen purification on a membrane module is illustrated in Fig. 1. After the
membrane module was designed and constructed to provide membrane module was assembled, it was installed in
easy assembly using a knife-edge sealing method. Neverthe- a furnace. A K-type thermocouple was fixed just on the upper
less, the module housing was also needed to avoid air contact. the surface of the membrane in the module in order to adjust
This housing complicates the configuration of modules and the temperature of the system. The gas flow was controlled by
lowers thermal efficiency. a mass flow controller (MFC, Brooks 5850E series, allowable
We designed a simplified, plate-type membrane module pressure: 20 bar). The pressure in the module was regulated by
for hydrogen purification with no needs for any type of
complicated bonding apparatus or housing. We successfully
constructed and tested a defect-free membrane module.

2. Experimental

2.1. Preparation of plate-type Pd-based membrane

The plate-type Pd-based membrane was prepared by magne-

tron sputtering method over a nickel metal support according to
our own method [4,8]. In order to fabricate the plate-type metal
support with a diameter of 50.0 mm, nickel powder (mean
diameter: 2.55 mm and purity: 99.8%) from Vale Inco Pacific Fig. 1 e Experimental schematic diagram for permeation
Limited was compressed without a binder in a cylindrical metal test in a membrane module.
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a pressure controller (Alicat Scientific) in the off-gas stream of assembled module was 15.6 cm2. As presented in Fig. 2,
the retentate side. Pure hydrogen from the permate/retentate a significant thin-film Pd-alloy membrane over a nickel
sides of the membrane was metered by a digital flow meter substrate was successfully prepared by controlling the surface
(ADM 2000, Agilent Technologies). roughness of the porous metal support.
The permeation measurements were performed in pure The layout (A) and photograph of components (B) of the
hydrogen at 350 and 400  C with no sweep gas. The hydrogen membrane module and photographs of the assembled module
flux (mol/cm2/sec) was calculated by dividing the flow into an (C) are shown in Fig. 3. The membrane module was designed
effective membrane area and selectivity was also presented with a double o-ring sealing mechanism which is suitable for
by the H2/He flow ratio. Before and after the permeation test, easier module assembly and ensured module-sealing. Gao
the module was heated in an Ar and He environment until the et al. [24] employed two soft copper gaskets to seal their high
desired temperature was reached, then the inert gases were temperature permeation cell. Here, the selection of o-ring
displaced with hydrogen gas. materials, graphite, cupper, etc., is important to apply to
a wide range of operating conditions (particularly, high
temperature and high-pressure). We have used two kinds of
3. Results and discussion o-ring, stainless steel o-ring and Au-coated one which allowed
the high-pressure operation. One stainless steel o-ring was
The photographs and FE-SEM images of prepared metal used for preventing an inflow of external oxygen which would
supports are shown in Fig. 2(aec). The surface roughness of damage the membrane. In order to ensure the inner sealing of
the support is important to coat the defect-free and thin-film hydrogen, an Au-coated metal o-ring was used, as gold has
membrane over it. The polishing process was thus applied to a relatively high mobility at low temperatures similar to Ag
reduce surface roughness for obtaining a better thin-layer and Cu metals, resulting in an improved seal of the membrane
membrane. The raw nickel plate had some pores as shown module. These were assembled carefully while tightening
in Fig. 2(a). The pores exposed on the surface of support dis- together bolts and nuts through the holes on the edges of the
appeared and there were deep scratches on the surface of flanges. The assembled module was checked with helium to
the manual polished nickel support as shown in Fig. 2(b). After confirm a tight seal and then placed in the electric furnace
the two-step polishing process as presented in Fig. 2(c), the without any housing or chamber as illustrated in Fig. 3. In
surface of the polished nickel support looked like a mirror and a simplified, plate-type membrane module, the permeation
its surface roughness was remarkably diminished. test was conducted with single gas of H2 as a function of
The photograph and FE-SEM images of the PdeCu coated transmembrane pressure difference at 350  C and 400  C as
membrane are shown in Fig. 2(d,e). A pinhole-free PdeCu displayed in Fig. 4. The hydrogen flux increased with the
membrane with a thickness of 2.8 mm was prepared on the temperature and pressure difference. As indicated by the
surface of a polished nickel support. EDX analysis indicated graph, a pure hydrogen flux at 2.1 MPa (P2, feed pressure) and
that the membrane consisted of 80% Pd and 20% Cu. The size 400  C was 0.98 mol/m2/s. For thick Pd membranes (Pd film
of PdeCu membrane shrank in the thermal treatment to thickness  10 mm), the rate-determining step for the perme-
49.9 mm and its effective area for hydrogen permeation in the ation process is the bulk metal diffusion of atomic hydrogen,

Fig. 2 e The photographs and FE-SEM images of prepared metal supports (a, b, and c) and the PdeCu coated membrane
(d and e).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 0 1 3 6 e1 0 1 4 0 10139

Fig. 3 e The layout (A) and photograph of components (B) of the membrane module and photographs of the assembled module (C).

for which the n-value should be 0.5 in equation of Sievert’s ideal H2/He selectivity at 400  C for a feed pressure of 0.5 MPa
Law [25]. As shown in Fig. 4, the linear regression of the data was over 5000.
gave an n-value of 0.56, indicating that very thin membrane
film was shown to cause deviation from that value. H2 per-
meance (mol H2/m2/s/Pa0.56) which is a slope in plots of H2 flux 4. Conclusions
4
vs. ðP0:56
2  P0:56
1 Þ was 2.57  10 for 350  C and 3.45  104 for
400  C, respectively. The R value for the best fit lines through
2
The simplified, plate-type membrane module for hydrogen
the SigmaPlot for the flux vs. ðP0:56
2  P0:56
1 Þ data was 1.0. The separation has been designed and constructed without any
type of complicated bonding apparatus or housing. A double
o-ring sealing mechanism was used for easier assembly and to
ensure module-sealing. The hydrogen permeation and helium
leak tests confirmed that the assembled membrane module
performs well. Specifically, the hydrogen permeation test was
conducted to 2.1 MPa (feed pressure) and showed a hydrogen
flux of 0.98 mol/m2/s at 400  C on the defect-free PdeCu
membrane with a thickness of 2.8 mm supported a polished
nickel metal. The assembled membrane module presents
a significant advance not only in protecting the membrane
from the module preparation procedures and air contact but
also during high-pressure operation. Furthermore, we suggest
that the simplified, plate-type membrane module is suitable
for application as a compact hydrogen purification system due
to simple assembly and easily stackable plate-type
membrane.

Acknowledgements

Fig. 4 e Hydrogen permeation flux as a function of the This work was supported by the New and Renewable Energy
transmembrane pressure at 350  C (white circle) and 400  C Technology Development Program (2008NHY08P030000)
(black circle). under the Ministry of Knowledge Economy, Republic of Korea.
10140 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 0 1 3 6 e1 0 1 4 0

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