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Journal of Membrane Science 310 (2008) 550556

Oxygen production using La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) perovskite hollow bre membrane modules
Xiaoyao Tan a, , Zhaobao Pang a , K. Li b,
a

School of Chemical Engineering, Shandong University of Technology, 12 Zhangzhou Road, Zibo, Shandong 255049, PR China b Department of Chemical Engineering and Technology, Imperial College London, South Kensington, London SW7 2AZ, UK Received 17 August 2007; received in revised form 12 October 2007; accepted 24 November 2007 Available online 5 December 2007

Abstract A phase-inversion/sintering technique has been employed in the production of La0.6 Sr0.4 Co0.2 Fe0.8 O3 (LSCF) hollow bre membranes, a bundle of which has then been placed in a high-temperature furnace for production of high purity oxygen from air at temperatures between 980 C and 1060 C. By applying a vacuum in the hollow bre lumens, a product stream containing oxygen purity of 97.15% has been obtained. The downstream vacuum degree higher than 99 kPa shows negligible effect on the oxygen production rate. Studies on long-term operation suggest that the LSCF hollow bre membranes are less stable for the oxygen production due to the segregation of the constituent membrane elements and the formation of new phases on the outer membrane surfaces. The effect of the operating cycle on the retrogression of membrane performance is much larger than that of duration used in a single cycle. 2007 Elsevier B.V. All rights reserved.
Keywords: Oxygen production; Hollow bre; Perovskite membrane

1. Introduction Oxygen production by air separation is of great importance in both environmental and industrial processes. It is usually realized by cryogenic distillation, pressure swing adsorption (PSA) or by polymeric membrane separation. These processes are either energy consumptive and very costly or unable to produce high purity of oxygen [1]. Alternately, dense ceramic membranes such as La1x Srx Co1y Fey O3 (LSCF) and Ba1x Srx Co1y Fey O3 (BSCF), which exhibit appreciable oxygen ionic and electronic conductivity, have become of great interest as a potentially economical, clean and efcient means to produce pure oxygen [27]. When an oxygen partial pressure gradient is imposed across these dense membranes at a high temperature, the oxygen may transport in the form of oxygen ions from the high partial pressure side to the low partial pressure side and released in the downstream without the need of electrodes and external electrical loadings, which makes the system very simple.
Corresponding author. Tel.: +86 533 2313676; fax: +86 533 2313676. Corresponding author. Tel.: +44 207 5945676; fax: +44 207 5945629. E-mail addresses: cestanxy@yahoo.com.cn (X. Tan), Kang.Li@Imperial.ac.uk (K. Li).

In recent years, ceramic hollow bre membranes have been successfully prepared using a phase-inversion/sintering technique [811]. Such hollow bre membranes may provide a much higher area/volume ratio (5009000 m2 /m3 ) than other congurations. Therefore, use of the hollow bre perovskite membranes is able to minimize the volume of membrane systems, leading to a reduced cost. In addition, it also makes the high-temperature sealing less problematic for assembly of membrane modules. In this study, we continue our earlier studies [1214] in production of a large hollow bre perovskite membrane module for oxygen separation from air with appreciable oxygen ux and purity. Vacuum operating mode has been adopted since it was found to be the best and economical operating mode for the oxygen production. The long-term operating performances and the post-operation analysis of the hollow bre membrane module have also been investigated experimentally in details. 2. Experimental 2.1. Preparation of LSCF hollow bre membranes LSCF hollow bre membranes were prepared by the phaseinversion/sintering technique. The detailed procedures were described elsewhere [8]. In this work, the starting suspension

0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2007.11.051

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was composed of 70.49 wt% LSCF powders (surface area of 9.53 m2 /g and d50 = 0.6 m, purity > 99.9%) purchased from Praxair Surface Technologies Corporation, 5.81 wt% polyethersulfone (PESf) [(Radel A-300), Ameco Performance, USA], 23.26 wt% 1-methyl-2-pyrrolidinone (NMP) [Synthesis Grade, Merck] and 0.44% polyvinyl pyrrolidone (PVP, K30) [from Fluka, Mw = 40,000]. A spinneret with the orice diameter/inner diameter of 3.0/1.2 mm was applied to fabricate the hollow bre precursors. Deionized water and tap water were used as the internal and external coagulants, respectively. Sintering was carried out at 1300 C (higher than previously used) for 5 h (longer than previously used), allowing for the formation of the complete gas-tight membranes, although this sintering condition may also eliminate inner nger-like structures, giving relatively symmetric structures. The prepared hollow bres have o.d./i.d. of 1.8/1.2 mm and length of 28 cm with a test-tube type and the open-end side was glued onto a stainless steel connector for suction. 2.2. Fabrication of the LSCF hollow bre membrane module To ensure that the hollow bre membrane module would not be leaking in oxygen production, all the hollow bres were individually tested to be gas-tight using a gas permeation apparatus developed by Tan et al. [13]. Seven gas-tight hollow bre membranes were glued onto a stainless steel connector on the open ends using an acidic silicone structural sealant (CJ-360), which can work well under the temperatures of 60 C to 343 C. Fig. 1 shows the hollow bre membrane module. 2.3. Oxygen production using the LSCF hollow bre membrane module An experimental set-up for oxygen production is schematically illustrated in Fig. 2. As can be seen, the hollow bre membrane module was placed under a vertically positioned

Fig. 1. Diagram of the LSCF hollow bre membrane module.

tubular furnace (diameter: 20 mm and height: 280 mm). An insulator was placed between inlet of the furnace from bottom and the connector of the membrane module so that the temperature at the sealing point is lower than that the sealant can withstand. The total length of the hollow bres positioned within the furnace tube is 22 cm. A claw rotor oil-free vacuum pump (2ZBL, purchased from Beijing Huaxiajia Sci. & Tech. Inc.) was connected to the outlet of the module. The operating vacuum degree was controlled using a frequency modulator (Suny3200, from Sunye Electric Co.) tted to the vacuum pump and was measured with a digital pressure sensor (PSA, from Autonics Co.). Another vacuum gauge was also used to monitor the vacuum degree. The oxygen concentration and the ow rate of the product were measured using an oxygen analyzer (TG-J310, from Xian Taige Analysis Instrument Inc.) and a digital lm ow meter (SF-1U/2U, purchased from Horiba Stec Co. Ltd.), respectively. During the experiments, the temperature was controlled using a temperature controller, where a K-type thermocouple with the tip positioned in the middle of the furnace and close to the centre of the furnace bore was used for the measurement of temperatures. At a given temperature, the oxygen concentration and the ow rate of the product stream were recorded at different vacuum degrees. 2.4. Characterizations of the membranes Crystallinity and phase purity of the hollow bre membranes were ascertained by X-ray diffraction (XRD) using a diffrac-

Fig. 2. Schematic diagram of the experimental set-up for oxygen production.

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Fig. 3. Temperature proles of the furnace at various setting temperatures.

tometer (BRUKER D8 ADVANCE, Germany) and employing Cu K radiation ( = 0.154178 nm). In preparing the samples for surface measurements, the used membranes removed from the reacted part (located in the middle of the furnace for oxygen permeation) were broken into small pieces. These membrane pieces were arrayed on the amorphous plasticene attached to the sample holder. In order to identify any changes of the crystalline structure on the membrane surfaces, a powder sample of the fresh membrane was also prepared to conduct XRD measurement. A continuous scan mode was used to collect 2 data from 10 to 80 with a 0.02 sampling pitch and a 2.4 /min scanning rate. The generator voltage and generator current were 40 kV and 40 mA, respectively. A eld emission scanning electron microscope system (FEI SIRION 200) was used to perform SEM analyses of the hollow bre membranes before and after the oxygen separation operations. Prior to characterization, Au was sputtered onto the sample surface so as to increase their conductivity. The elemental compositions of the membranes were determined by energy dispersive spectroscopy (EDS) using an Oxford Instruments Inca X-sight energy apparatus attached to the above-mentioned SEM system. 3. Results and discussion 3.1. Temperature proles in the furnace tube Prior to the oxygen production experiments, the temperature proles of the furnace were measured to ascertain the effective heating zone. A K-type thermocouple was used to measure the temperatures along the furnace bore when the furnace was set and controlled at a given temperature using a temperature controller. The temperatures were determined by measuring the electrical potential difference of the thermocouple using a potentiometric recorder, starting from the bottom inlet of the furnace. The temperature proles in the furnace at various setting temperatures were plotted in Fig. 3. As can be seen, the temperature prole curves are of parabolic form but not symmetric with respect to the height of the furnace bore because of the vertical installation. At lower controlling temperatures, the effective heating sector (or constant temperature zone) is located at the upper section of the furnace, but gradually shifts to the lower section as the setting temperature increases. In the meantime, the length of the effective heating zone is also decreased with

increasing the setting temperature. For instance, the effective heating sector lies between 9 cm and 18 cm away from the bottom inlet at the controlling temperature of 800 C. When the controlling temperature is increased to 1000 C, the effective heating zone then moves to the section between 8 cm and 16 cm away from the bottom inlet. In this study, the oxygen production was generally carried out at around 1000 C. Therefore, the length of the effective heating zone is around 8 cm, namely from 8 cm to 16 cm away from the bottom inlet. This means that the actual membrane area for oxygen production is about ca. 26 cm2 calculated by A = nL(do di )/ln(do /di ), in which n, L, do and di are the number, the length, the outer diameter and inner diameter of the hollow bre membranes, respectively. The temperature at the bottom entrance of the furnace is much lower than 350 C at the setting temperature of 1000 C, as shown in the gure. Moreover, there is a distance of 46 cm from the bottom entrance of the furnace to the sealing point and a heating insulator located between them, the temperature at the sealing points is much lower than that the silicone sealant can withstand, i.e., 343 C. 3.2. Performances of the LSCF hollow bre membrane module Performances of the LSCF hollow bre membrane module were investigated by varying the operating temperature and the vacuum degree, where the vacuum degree is dened as that the atmospheric pressure (101.3 kPa) minus the absolute pressure at the downstream. Obviously, the higher the vacuum degree, the lower the downstream oxygen partial pressure. All the data in this section were collected after the membrane module had worked steadily for 3 h. Fig. 4 shows the oxygen production performance of the LSCF hollow bre membrane module at different temperatures, where the oxygen production rate and the

Fig. 4. Performances of the LSCF hollow bre membrane module for oxygen production.

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product concentration are plotted against the applied vacuum degree. As is expected, the oxygen production rate increases with increasing the downstream vacuum degree, because the driving force for oxygen permeation is increased when the upstream oxygen concentration is constant, i.e., 21%. However, as the downstream vacuum degree is increased from 98 kPa to 98.5 kPa, the increase in oxygen production rate is very little especially at higher temperatures. This implies that further increasing the vacuum degree to higher than 99 kPa is not necessary because it contributes little to improving the oxygen production rate but leads to the remarkable increase in operation cost. In addition, the experimental data also show that the oxygen production rate increases as the operating temperature is increased. This is because the membranes oxygen permeability increases with temperature and the effective membrane area for oxygen permeation is also increased. At the setting temperature of 1060 C (the real temperature is around 1035 C), the oxygen permeation rate reaches 78.47 cm3 /min and the corresponding oxygen concentration attains up to 97.15%. This means that each hollow bre membrane contributed 11.2 cm3 /min to the overall oxygen production rate. Although the mixed conducting ceramic membranes are theoretically 100% permselective to oxygen, the highest oxygen concentration in the product stream was only 97.15%, as shown in Fig. 4(B). This implies that there is minor leakage in the membrane system, leading to entry of some nitrogen into the product stream. However, because the leakage increases more slowly than the oxygen permeation rate, the oxygen concentration in the product stream still increases with increasing the temperature and the applied vacuum degree, just as shown in Fig. 4. Assuming that the nitrogen enters into the product stream along with air, the leakage rate can be calculated by = 1y V 0.79 (1)

Fig. 6. Long-term operation of the LSCF hollow bre membrane module (1000 C and 95.5 kPa for Section II; 1000 C and 98.6 kPa for Sections IIIV).

peratures. It should be mentioned that the minor leakage could not be detected before high-temperature operations. 3.3. Long-term operation of the membrane module A long-term operation test was performed on the hollow bre membrane module with the results in the following. After the performance investigation, the operation was hold on for up to 260 h with the same LSCF hollow bre membrane module. Fig. 6 shows the oxygen production rate and the oxygen concentration as a function of operation time. As can be seen, the total operation process can be approximately divided into ve sections. Section I, from zero to t = 12 h, represents the performance investigation described above. In this section, many experimental data have been obtained but they are not becomingly plotted in the gure because the temperature and the downstream vacuum were changed frequently with time. In Section II, from t = 12 h to 82 h, the system was operated at 1000 C and 95.5 kPa. It

where V and y are the product ow rate cm3 /min, and the oxygen fraction in the product stream, respectively. Fig. 5 shows the air leakage calculated from the above equation as a function of vacuum degree at various temperatures. It can be seen that the leakage ranges from 1.5 mL/min to 2.8 mL/min, increasing not only with the applied vacuum degree but also with the operating temperature. It implies that the minor leakage is possibly due to the tiny defects presented on the hollow bre membranes or at the silicone sealant joint. The nitrogen may enter into the oxygen product stream through these defects by diffusion at higher tem-

Fig. 5. Air leakage of the membrane module.

Fig. 7. Effect of operating cycle on the membrane performances.

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Fig. 8. SEM images of the hollow bre membrane: (A) central dense layer of the fresh membrane; (B) outer surface of the fresh membrane; (C) inner surface of the fresh membrane; (a) central dense layer of the used membrane; (b) outer surface of the used membrane; (c) inner surface of the used membrane.

can be seen that the oxygen production rates are always lower than that measured in Section I under the same conditions, i.e., 42.21 cm3 /min. This suggests that the membranes performance has been decreased after the performance investigation. Furthermore, the oxygen production rate in the whole duration of around 70 h in this section declines slowly with time while the oxygen concentrations are varied between 95.7% and 96.52%. In Section III, from t = 82 h to 122 h, both the oxygen production rate and the oxygen concentration in the product stream are decreased noticeably although the downstream vacuum was increased to 98.6 kPa while the setting temperature was kept at 1000 C. This result is due to the fault of the thermocouple, making the real temperature for oxygen permeation much lower than the setting value (1000 C). After the faulty thermocouple was replaced with a new one, both the oxygen production rate and the oxygen concentration, as shown in Section IV, are getting back to the same ranges as in Section II. It can be seen that the oxygen production rates in the whole Section IV are seemly kept constant while the oxygen concentration is decreased slightly. Although

the oxygen production rate and the oxygen concentration are close to the values obtained in Section II, the membrane performance has actually been slightly deteriorated since the applied vacuum degree is higher than that in Section II. In Section V, from t = 230 h to 260 h, the oxygen production rate is steadily increased although the setting temperature and the downstream vacuum were remained the same as in Section IV. This result may possibly due to the slow enlargement of the minor defects after the long-term operation at high temperatures. In fact, the operation had to be stopped at t = 260 h because a small hole (large defect) was formed on one of the hollow bres (observed after post-mortem analysis). The reason for its occurrence is that the hollow bres may have thinner spots. Under high temperatures, such thin spots cannot withstand the pressure difference (1 atm) for long term. By a detailed analysis of the above longevity experiment, it seems that the decline in oxygen production rate is primarily due to the restarting of the membrane system. Therefore, the effect of the operating cycle, which is dened as a whole operating

X. Tan et al. / Journal of Membrane Science 310 (2008) 550556 Table 1 EDS analysis of the LSCF hollow bre membranes (atom percentage) Outer surface of the fresh membrane C O Fe Co Sr La 17.77 55.58 10.31 2.17 6.24 7.93 Outer surface of the used membrane 34.51 47.64 4.34 3.85 5.77 3.89 Inner surface of the fresh membrane 58.90 16.42 3.26 8.21 13.21 Inner surface of the used membrane 53.66 19.76 3.60 7.41 15.57

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Crystallite debris on the outer membrane surface 13.14 55.43 8.45 15.40 3.28 4.31

process from heating up the module from room temperature, collecting experimental data at high temperatures to cooling the module back to the ambient temperature, was also studied using a new seven-bre membrane module. The experimental results are shown in Fig. 7, where the oxygen production rate and the oxygen concentration in every single cycle are plotted against the operation time. The operating conditions for cycles 16 are the same, namely, the setting temperature and the applied downstream vacuum degree are 1000 C and 98.5 kPa, respectively, while for cycle 7 the setting temperature is 1020 C. It can be seen that the oxygen production rates are declined every time the system is restarted while the oxygen concentrations in the product stream are between 93% and 97%. For cycle 1, the oxygen production rate is increased with time up to the maximum value and then kept constant, but the oxygen concentration increases all the time. However, for other cycles, the oxygen production rate is always decreased slightly with the operation time. Obviously, the effect of the operating cycle on the retrogression of membrane performance is much larger than the duration time in the single cycle. 3.4. Post-operation analysis of the hollow bre membranes As described above, the LSCF hollow bre membranes were not very stable during the oxygen separations. In order to elucidate the reasons causing the decline of the membrane performance, SEM, EDS and XRD analysis of the hollow bre membranes were performed with the results given below. The membrane samples for the used membranes were taken from the reacted part (located in the middle of the furnace) after the long-term oxygen separation. In Fig. 8, micrograph images of the bulk membrane (central dense part on the cross-sectional fracture surface of the hollow bres), the inner surface and the outer surface of the used membranes are presented, which were marked by A, B and C, respectively. For comparison, SEM images of the fresh membranes at the three positions are also presented in the gure denoted by a, b and c, respectively. As can be seen, the surfaces at the three positions do not reveal obvious microstructural changes after the long-term operation. Most LSCF crystallite particles either in the used membrane or in the fresh membrane are larger than 1 m instead of the original powder size of around 0.3 m. It suggests that the size of the LSCF crystallites was changed during the membrane preparation (sintering stage) but not during the oxygen separation. However, after the long-term operation,

some crystallite debris was produced on the outer surface of the membranes, as shown in Fig. 8(b). In the meantime, there are also many ne crystallites formed on the inner membrane surface that appear much brighter, as shown in Fig. 8(c). Is it the formation of these ne crystallites to deteriorate the performances of the LSCF hollow bre membranes? To answer this question, qualitative EDS analysis was further performed to indicate the approximate element percentage presence and the possible stoichiometry changes after the oxygen separation. EDS analysis of the used and the fresh membranes with respect to both the inner and the outer surfaces is summarized in Table 1. It shows that no carbon is presented on the inner surfaces of either the used membrane or the fresh membrane. Moreover, no signicant stoichiometry changes are observed on the inner membrane surface after the oxygen separation. However, carbon is presented on the outer surfaces of both the used and the fresh membranes. After the long-term oxygen separation, carbon content is even increased from 17.77% to 34.51% in atom percentage. Furthermore, it is also observed that the most significant stoichiometry changes of the membrane occur with respect to cobalt. For instance, the ratio of Co to Fe in the fresh membrane is 1:4.75, which is close to the original stoichiometry. But it is changed to 1:12 after the long-term oxygen separation. In addition, the approximate element percentage of the crystallite debris produced on the membrane outer surface is also given in Table 1. It can be seen that the ratio of Co to Fe even reaches to 1.82:1. This indicates that segregation of the constituent membrane elements occurred during the oxygen separation [15,16], and cobalt is the fastest element moving towards the membrane outer surface. A more detailed analysis of the deterioration of LSCF membranes will be performed in the near future. Fig. 9 shows the XRD patterns of the inner and outer surfaces of the used membranes, in which the powder XRD pattern of the fresh membrane is also presented for comparison. It can be seen that the inner membrane surfaces have retained the perovskite structure, but additional peaks to the perovskite phase (indicated by p) have been produced on the outer membrane surfaces. It indicates that new phases have been formed on the membrane outer surfaces due to the segregation of constituent membrane elements, such as SrO (PDF reference code 27-1304) and Fe2 O3 (PDF reference code 21-0920) [1517]. The phase separation is attributed to the kinetic decomposition of the membrane material and arises from the non-negligible cation mobilities at operating temperatures [16]. In addition, some carbonates such as La2 CO5 (PDF reference code 25-0423) and CoCO3 (PDF refer-

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Natural Science Foundation of China (NNSFC, No. 20676073) and EPSRC in the United Kingdom (GR/S12203). References
[1] J. Luyten, A. Buekenhoudt, W. Adriansens, J. Cooymans, H. Weyten, F. Servaes, R. Leysen, Preparation of LaSrCoFeO3x membranes, Solid State Ionics 135 (2000) 637. [2] V.V. Kharton, A.A. Yaremchenko, A.V. Kovalevsky, A.P. Viskup, E.N. Naumovich, P.F. Kerko, Perovskite-type oxides for high-temperature oxygen separation membranes, J. Membr. Sci. 69 (1999) 163. [3] H. Wang, R. Wang, D.T. Liang, W. Yang, Experimental and modeling studies on Ba0.5 Sr0.5 Co0.8 Fe0.2 O3 (BSCF) tubular membranes for air separation, J. Membr. Sci. 243 (2004) 405. [4] P.N. Dyer, R.E. Richards, S.L. Russek, D.M. Taylor, Ion transport membrane technology for oxygen separation and syngas production, Solid State Ionics 134 (2000) 21. [5] S. Li, W. Jin, N. Xu, J. Shi, Synthesis and oxygen permeation properties of La0.2 Sr0.8 Co0.8 Fe0.2 O3 membranes, Solid State Ionics 124 (1999) 161. [6] D. Stefan, J.V. Herle, Oxygen transport through dense La0.6 Sr0.4 Fe0.8 Co0.2 O3 perovskite-type permeation membranes, J. Eur. Ceram. Soc. 24 (2004) 1319. [7] S.J. Xu, W.J. Thomson, Oxygen permeation rates through ion-conducting perovskite membranes, Chem. Eng. Sci. 54 (1999) 3839. [8] X. Tan, Y. Liu, K. Li, Preparation of La0.6 Sr0.4 Co0.2 Fe0.8 O3 hollow bre membranes for oxygen production by a phase-inversion/sintering technique, Ind. Eng. Chem. Res. 44 (2005) 61. [9] K. Li, X. Tan, Y. Liu, Single-step fabrication of ceramic hollow bres for oxygen permeation, J. Membr. Sci. 272 (2006) 1. [10] S. Liu, G. Gavalas, Oxygen selective ceramic hollow bre membranes, J. Membr. Sci. 246 (2005) 103. [11] T. Schiestel, M. Kilgus, S. Peter, K.J. Caspary, H. Wang, J. Caro, Hollow bre perovskite membranes for oxygen separation, J. Membr. Sci. 258 (2005) 1. [12] X. Tan, K. Li, Modeling of air separation in a LSCF hollow-bre membrane module, AIChE J. 48 (2002) 1469. [13] X. Tan, Y. Liu, K. Li, Mixed conducting ceramic hollow bre membranes for air separation, AIChE J. 71 (2005) 1991. [14] X. Tan, K. Li, Oxygen production using dense ceramic hollow ber membrane modules with different operating modes, AIChE J. 53 (2007) 838. [15] J.E. ten Elshof, H.J.M. Bouwmeester, H. Verweij, Oxygen transport through La1x Srx FeO3 membranes. I. Permeation in air/He gradients, Solid State Ionics 81 (1995) 97. [16] R.H.E. van Doorn, H.J.M. Bouwmeester, A.J. Burggraaf, Kinetic decomposition of La0.3 Sr0.7 CoO3 perovskite membranes during oxygen permeation, Solid State Ionics 111 (1998) 263. [17] I. Iguchi, N. Sata, H. Yugami, H. Takamura, Oxygen permeation properties and the stability of La0.6 Sr0.4 Fe0.8 Co0.2 O3 studied by Raman spectroscopy, Solid State Ionics 177 (2006) 2281. [18] J.E. ten Elshof, H.J.M. Bouwmeester, H. Verweij, Oxygen transport through La1x Srx FeO3 membranes. II. Permeation in air/CO, CO2 gradients, Solid State Ionics 89 (1996) 81. [19] S. Lee, S.K. Woo, K.S. Lee, D.K. Kim, Mechanical properties and structural stability of perovskite-type, oxygen-permeable, dense membranes, Desalination 193 (2006) 236.

Fig. 9. XRD of the hollow bre membranes: (A) fresh membrane powders; (B) inner surface of the used membrane; (C) outer surface of the used membrane.

ence code 01-1020) have also been produced on the membrane outer surfaces because of the presence of carbon dioxide in the air [1719]. As a result, the carbon content is noticeably increased after the long-term oxygen separation, as described above. 4. Conclusions Oxygen production using the LSCF hollow bre membrane modules has been investigated experimentally. A product stream with the oxygen purity as high as 97.15% has been obtained using the established membrane system with applying a vacuum in the hollow bre lumens. However, the downstream vacuum degree higher than 99 kPa gives negligible effect on the oxygen production rate. The LSCF hollow bre membranes are found to be less stable for the long-term oxygen production due to the segregation of the constituent membrane elements and the formation of carbonates on the outer membrane surfaces. The effect of the operating cycle on the retrogression of membrane performance is much larger than that of operating duration in a single cycle. Acknowledgements The authors gratefully acknowledge the research funding provided by the National High Technology Research and Development Program of China (No. 2006AA03Z464), National