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School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160, China
School of Chemical Engineering, Shandong University of Technology, Zibo 255049, China
Department of Chemical Engineering and Technology, Imperial College London, South Kensington, London SW7 2AZ, UK
a r t i c l e
i n f o
Article history:
Received 19 October 2009
Received in revised form 1 January 2010
Accepted 4 February 2010
Available online 11 February 2010
Keywords:
Oxygen production
Hollow bre
Perovskite
Mixed conducting membrane
a b s t r a c t
La0.6 Sr0.4 Co0.2 Fe0.8 O3 (LSCF) hollow bre membranes prepared by a phase-inversion/sintering technique were assembled into a membrane system to produce oxygen of high purity (>99%) from air at
elevated temperatures. The separation performances, stability, scaling-up effect and the energy consumption of the membrane system were investigated both theoretically and experimentally. The membrane
system containing 889 hollow bres could yield maximum 3.1 L(STP) min1 oxygen with the purity of
99.9% at 1070 C and 98.5 kPa vacuum degree, but the temperature higher than 1070 C would lead to
the system failure. It showed the potential of much higher production rates only if the high-temperature
sealing problem could be solved. When operated at around 960 C, the system exhibited more than 1167 h
longevity with the oxygen production rate of 0.84 L(STP) min1 and oxygen purity of 99.4%. The energy
consumption of the system increased with operating temperature but the energy consumption per unit
oxygen product decreased with increasing the operating temperature and the effective membrane areas.
In order to reduce the oxygen cost to commercial level, heat exchangers have to be integrated in the
membrane system to recover the heat energy in both the exhaust gas and the oxygen product. The oxygen recovery should be limited within 2040% for the sake of both energy and membrane area savings.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Oxygen production from air is of great importance in both
environmental and chemical industries. It is usually achieved
by cryogenic distillation, pressure swing adsorption (PSA) or by
polymeric membrane separation. These processes are either of
high energy consumption or unable to produce oxygen of high
purity. Alternately, dense mixed conducting membranes such as
La1x Srx Co1y Fey O3 (LSCF) perovskite which exhibit appreciable oxygen ionic and electronic conductivity have become of great
interest as a potentially economical, clean and efcient means of
high pure oxygen production [17]. When an oxygen partial pressure gradient is imposed across such dense membranes at a high
temperature (usually >700 C), the oxygen may be transferred from
the high partial pressure side to the low partial pressure side without the need of electrodes and external electrical loadings, making
the membrane system and operation much simplied.
In recent years, perovskite hollow bre membranes have
been successfully prepared by a phase-inversion/sintering process
Corresponding author. Tel.: +86 533 2786292; fax: +86 533 2786292.
E-mail address: cestanxy@yahoo.com.cn (X. Tan).
0376-7388/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.02.015
190
Fig. 1. Photos of (a) the LSCF hollow bre membranes; (b) the hollow bre bundles; and (c) the hollow bre membrane module.
Fig. 2. Hollow bre membrane system for oxygen production (A) ow chart; and
(B) photo of the setup.
191
192
Fig. 5. Effect of vacuum degree on the performance of the hollow bre membrane
system (889-bre module).
193
Fig. 9. Heating power of the furnace in the 889-bre membrane system at different
operating temperatures.
(1)
Fig. 10. Diagram of the membrane system with heat exchange (A) between the air
feed and the oxygen stream; (B) between the air feed and the exhaust stream; and
(C) between air feed and both the exhaust and oxygen streams.
194
Am = 1 m2
0.18 cm
0.12 cm
= 2.0
98.3 kPa
0.2 Nm3 min1
25 C
50 C
8501050 C
0.8
kf
kr = 2.07 10 exp
where FAir and FO2 are the air feed ow rate and the oxygen production rate, respectively; xe is the oxygen fraction in the furnace
tube and exhaust stream. For the catalytically modied hollow bre
membrane, the oxygen production rate may be given by [17]:
kr [(p1 xe )
FO2 = Am
(cm2 /s)
0.5
= 1.85 104 exp 27291
(cm/Pa
s)
T
29023
4
2
0.5
0.5
(p2 )
0.5
0.5
(mol/cm s)
(2)
where Am is the membrane area of the hollow bre module; the
permeation enhancement factor by catalytic modication; p1 and
p2 are the upstream and downstream pressures (p2 = pa operating
vacuum degree where pa is atmospheric pressure), respectively; Rm
the logarithmic radius, Rm = (Ro Rin )/ln(Ro /Rin ), in which Ro and Rin
are respectively the outer and the inner radius of the bre; DV is the
diffusion coefcient of oxygen vacancy; kf and kr are, respectively,
the forward and the reverse reaction rate constants for the surface
exchange reaction:
kf /kr
x + 2h
+ VO OO
1
O
2 2
(3)
FO2 CpO2 (50 25) + [(0.21FAir FO2 )CpO2 + 0.79FAir CpN2 ] (T 25)
0.9
(4a)
(B): heat exchange between the air feed and the exhaust stream
only
Q2 =
FO2 CpO2 (T 25) + [(0.21FAir FO2 )CpO2 + 0.79FAir CpN2 ] (50 25)
0.9
(4b)
(C): heat exchange between the air feed and both the exhaust and
oxygen streams
Q3 =
FO2 CpO2 (T 25) + [(0.21FAir FO2 )CpO2 + 0.79FAir CpN2 ] (50 25)
0.9
(4c)
where Cpi is the specic heat capacity of gas species i; T is
the temperature of the air feed after heating by the exhaust
stream,
T =
(T 50) + 25
(5)
ln
p
a
p2
(6)
Fig. 11. Energy consumption of the oxygen product by the membrane system with
heat exchange (A) between the air feed and the oxygen stream; (B) between the air
feed and the exhaust stream; and (C) between air feed and both the exhaust and
oxygen streams.
195
Nomenclature
Fig. 12. Plot of the energy consumption of oxygen product and membrane area
against oxygen recovery (air feed = 0.2 Nm3 min1 ).
be seen, the oxygen production cost of the membrane process cannot be reduced to the PSA cost level unless the heat in exhaust
gas is recovered by performing heat exchange between the air
feed and the exhaust stream. In addition, the energy consumption
per unit oxygen product by the membrane system can be reduced
by either increasing the operating temperature or increasing the
membrane areas. Since the energy consumption of the membrane
system is mainly the residual heat along with the exhaust and product streams, it can be reduced by decreasing the amount of exhaust
gas for a given air feed. In another word, it is necessary to increase
the oxygen recovery so as to reduce the oxygen cost. This can be
achieved by increasing the operating temperature and the membrane areas. Fig. 12 plots the energy consumption per unit oxygen
product and the required membrane area against oxygen recovery
which is dened as:
=
FOx
100%
0.21FAir
(7)
Am
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