Microporous and Mesoporous Materials 85 (2005) 313323 www.elsevier.

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Synthesis and CO2/N2 gas permeation characteristics of ZSM-5 zeolite membranes

Dong Wook Shin a, Sang Hoon Hyun
a

a,*

, Churl Hee Cho b, Moon Hee Han

School of Advanced Materials Engineering, Yonsei University, 134 Shinchon-dong, Seodaemoon-gu, Seoul 120-749, Republic of Korea b Functional Materials Research Center, Korea Institute of Energy Research, Taejon 305-343, Republic of Korea Received 21 September 2004; received in revised form 28 June 2005; accepted 29 June 2005 Available online 22 August 2005

Abstract ZSM-5 zeolite membranes for CO2 separation have been synthesized via hydrothermal-treating various porous a-alumina tubes in template reaction mixtures. The eect of each support acted as an Al source in high pH solution during hydrothermal treatment, and of the SiO2 molar ratio in reaction mixtures on the formation of ZSM-5 crystalline layers was investigated. The synthesized membranes were also surface-modied by dip-coating with polymeric silica sol which lled up the intercrystalline voids in order to improve the CO2 separation eciency. The ZSM-5 zeolite membranes have been evaluated by the CO2/N2 separation factor and permeance measured as a function of the stage cut, the helium sweeping rate, the feed pressure, and the permeation temperature. The maximum separation factor of the ZSM-5 zeolite membrane for a CO2/N2 (50% CO2) gas mixture was about 54.3 at 25 C and 14.9 at 100 C, respectively, and its permeance was 3.6 108 mol/m2 s Pa. In particular, it was found that the separation factor of the ZSM-5 zeolite membranes were nearly independent of the moisture in the feed. 2005 Elsevier Inc. All rights reserved.
Keywords: Hydrothermal treatment; ZSM-5 zeolite membrane; Porous a-alumina tubes; CO2 separation; Surface-modication

1. Introduction Since the greenhouse eect created by the accumulation of carbon dioxide in the atmosphere is threatening to human life, continued research to eciently separate carbon dioxide emitted mainly by high temperature systems is necessary. Polymer membranes cannot be used at high temperatures because of their low thermal stability. MFI zeolite membrane among inorganic membranes is promising because of its high thermal, chemical and mechanical stabilities, hydrophobic property, long-life application, and high adsorption capacity of CO2 (i.e. silicalite-1 and ZSM-5) [1,2]. A MFI-type zeolite membrane can be generally synthesized in an aqueous solution including organic templates by the hydrothermal
*

Corresponding author. Tel.: +82 2 2123 2850; fax: +82 2 365 5882. E-mail address: prohsh@yonsei.ac.kr (S.H. Hyun).

treatment. In this work, both tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) were used as templates for the optimization of synthetic composition because TPA, OH, and oxyanion (Br) show dierent crystallinity and crystal size. Also, the H2O/OH ratio and the addition of certain oxyanions of group VA and VIIA in the periodic table signicantly aect the crystallization of MFI zeolite [3,4]. These synthesized membranes have to be calcined to remove organic templates that block the zeolite channels. During this calcination, the probability of micro defects is high because of the dierence between the thermal expansion coecients of a-alumina and zeolite frame work and the phase transition of zeolite crystals [5,6]. In recent ports, MFI membranes are prepared to separate isomers and hydrocarbon series mainly using the

1387-1811/$ - see front matter 2005 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2005.06.035

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pervaporation process [614]. MFI membranes for CO2 separation are limited because (i) a very small eective area and a low separation eciency has no relation to practical usage, (ii) many research studies of MFI membranes are reported only as CO2/N2 ideal selectivity (i.e. each single gas ux ratio), and (iii) a high separation eciency is not shown at high temperatures. Bonhomme et al. [7] reported the preparation of ZSM-5 zeolite membranes using high silica synthesis gel on silicalite seeded a-alumina tubes. But the CO2 to air separation factor was as low as 3. In addition, repeated hydrothermal treatment was performed on a dense membrane layer. Li et al. [8,9] and Lai and Gavalas [15] reported the preparation of ZSM-5 zeolite membranes with organic-free mixtures. Seeded supports were synthesized by organic-free hydrothermal treatments, and the calcination process was not required. Nevertheless, the studies show that the CO2 separation was not achieved. Li et al. [16] and Tomita et al. [17] reported high CO2/ CH4 separation eciencies using SAPO-34 membranes and DDR-type zeolite membranes, respectively; however, they did not report on the CO2/N2 separation factors in the CO2/N2 gas mixture system. Zhang et al. [10] reported that iron (Fe) component has an inuence on the preparation of ZSM-5 zeolite membranes. When the concentration of Fe component is low, a good eciency of ZSM-5 zeolite membrane is attained. Actually, if a teon-lined autoclave is not used and a stainless steel autoclave is used, unwanted materials like Fe component may badly aect the formation of zeolite membranes. In this research, however, the synthesis of the ZSM-5 zeolite membrane, which was in a stainless steel autoclave, did not have trouble which might be caused by contaminants. On the contrary, the synthesized membranes in a teonlined autoclave showed low CO2 separation eciencies because the eect of Fe component may be negligible in our experiment. Moreover, the proper temperature for the synthesis of ZSM-5 zeolite membrane might not be reached by the low thermal conductivity of the teon vessel. Except for MFI zeolite membranes, NaY zeolite membranes show high separation eciency for CO2. Although Kusakabe et al. [1821] reported that in the ion-exchanged NaY zeolite membranes, which show high CO2 separation eciencies, the eective area of the membrane is very small. Moreover, the NaY zeolite membrane shows less thermal and mechanical stabilities because of the low Si/Al ratio. Low Al content is reported to give a good reproducibility and chemical stability. Although MFI zeolite has a lower adsorption capacity for CO2 than NaY, the adsorption eects are less pronounced at high loading of CO2 because of the hindrance of CO2 to N2 in the zeolite channel. Also MFI zeolite is less aected by moisture even at low tem-

peratures because of the limited hydrophilicity of the MFI zeolite. Bernal et al. [22] and Ali et al. [23] reported that the ion exchange process of MFI zeolite membranes improved the separation eciency of the membranes. The ion exchange processes are thought to control channel size and chemical adsorption properties (i.e. a weak adsorption force, which is adequate to an operation temperature is required to separate CO2 eciently in a CO2/N2 gas mixture). Synthesis of the zeolite layer on one side of the support surfaces alone can improve the permeance and the separation factor. If the zeolite layer is synthesized on both sides of the support, the permeance and the separation factor are decreased because (i) the thickness of zeolite layer is doubled, (ii) the rst zeolite layer (feed side) operates in the hole area, but the available area of the second zeolite layer (permeate side) is limited to the porosity of support, and (iii) N2 gas already permeated through the rst zeolite layer badly aects the gas separation eciency by its existence of itself between two zeolite layers. In this study, the ZSM-5 zeolite membrane synthesized on one side of the support surfaces was not treated because of the diculties in sealing either the inner or the outer side of the tube-type alumina support. The present paper reports on the preparation of both-sided ZSM-5 zeolite membranes synthesized with high thermal stability, good separation factor, and good permeance for CO2.

2. Experimental 2.1. Supports and reacting solution Porous a-alumina tubes of four types with a length of 90 mm were used as membrane supports. For studying the eects of membrane support type on the synthesis of ZSM-5 zeolite membrane, S-A, S-B, S-C, and S-D were studied, where S-A stands for a slip-casted support, S-B for Nanopore support, S-C for 0.2 lm Ceracomb support, and S-D for 0.8 lm Ceracomb support. Its outer diameter and thickness are S-A: 8 mm and 0.8 mm/ S-B: 7.5 mm and 1 mm/S-C: 10.3 mm and 1.7 mm/ S-D: 10.3 mm and 1.7 mm, respectively. The slip-casted supports (S-A) were fabricated by the usual slip-casting procedure using the slurry of a-alumina powder (AES11, Sumitomo) [24]. Supports were cleaned three times in an acetone washing for 10 min and then heat-treated at 500 C for 4 h. The supports were hydrothermally treated using a template solution. The clear template solution for the synthesis of ZSM-5 zeolite membranes was prepared according to the following procedure. First, the measured amounts of NaOH (98 wt% NaOH, Junsei), TPAOH (1 M tetrapropylammonium hydroxide, Aldrich), and

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315

TPABr (98 wt% tetrapropylammonium bromide, Aldrich) were dissolved in a measured amount of de-ionized water. This solution was then added in drops into a colloidal silica sol (40 wt% SiO2, Ludox AS-40, Aldrich) while stirring. The sol was ltered using a lter paper (No. 4, Whatman) to remove silica akes and other contaminants before use. The nal solution was stirred at room temperature for about 1 day. The initial high viscosity and milky color characteristics of the solution changed to a clear solution with a low viscosity. After aging for 1 day, this clear template solution with the molar composition of xSiO2:1.2NaOH:0.15TPAOH: 0.15TPABr:140H2O was prepared by ltering with a lter paper (No. 4, Whatman). 2.2. Preparation of ZSM-5 zeolite membrane The support was put vertically in a tubular type stainless steel autoclave (40 mm of inner diameter, 140 mm of length). After adding 120 ml of the reaction solution, the autoclave was placed in a convection oven (Jeio Tech.) preheated to 185 C. The hydrothermal treatment was performed at 185 C for 40 h. After the hydrothermal treatment time, the autoclave was cooled with tap water to room temperature. The synthesized membrane was washed with de-ionized water and then dried at room temperature overnight and then at 120 C for 2 h. After drying, the membrane was tested for N2 permeation because a well-synthesized membrane should be imperme-

able before calcination. The dried membrane was calcined at 450 C for 12 h using a ramp rate lower than 1 C/min. Polymeric silica sol was prepared from TEOS (tetraethoxysilane, Fluka) dissolved in ethanol using a twostep acid/base catalyzed process. First of all, TEOS, ethanol, H2O, and 1 M HCl were mixed with molar ratios of 1:4:1:0.007 and reuxed at 60 C for 90 min while stirring. In the second step, 0.05 M NH4OH, former sol, and ethanol were mixed in the volume ratios of 1:10:44 and stirred for 60 min. The synthesized membrane was dipped into the polymeric silica sol in 1 min dwelling time and at 4.5 cm/min drawing rate. That surfacemodied membrane was dried at room temperature for 4 h then at 200 C for 2 h.

2.3. Evaluation of gas permeation property CO2/N2 permeance and separation factor through ZSM-5 zeolite membrane were evaluated for equi-molar CO2/N2 gas mixture. A prepared ZSM-5 zeolite membrane was connected with impermeable stainless tubes using epoxy resin (Ceracot) at both sides. That connected membrane was installed into a stainless steel cell (Fig. 1(a)) for the gas permeation tests. The permeation temperature was controlled by an electric heating mantle. Fig. 1(b) shows a moisture-saturated apparatus. Original CO2/N2 mixed feed gas penetrates through pure

Feed gas Epoxy resin Stainless steel tube

Sweep gas

Permeate gas

O-ring Zeolite membrane

Electric heating at mantle

Retentate gas

Feed gas

Moisture-saturated feed gas

Water
b
Fig. 1. Schemes for (a) the permeation test cell and (b) apparatus for moisture saturation of the feed gas.

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water and then moisture-saturated feed gas was injected into the permeation test cell. To investigate the eect of the operation temperature, the membrane was held at the desired temperature for approximately 2 h. Helium gas was used as a sweep gas which was introduced to the permeate side of the membrane. Every gas permeance was evaluated by a gas ow meter (Humonics). The separation factor for CO2/N2 gas mixture was calculated by a gas chromatograph (GC-680D, Youngin).

3. Results and discussion 3.1. Characterization of a-alumina supports Slip-casted support has sleeker surface/fracture morphology and uniform microstructure than purchased extrusion supports (S-BD) as shown in Fig. 2. On the other hand, extrusion supports have large a-alumina particles, rough morphologies, and non-uniform microstructures progressing from S-B to -D.

Fig. 2. SEM images for top and fracture surfaces of tubular a-Al2O3 supports: S-A; slip-casted support (pore size 0.1 lm), S-B; extrusion support (pore size 0.1 lm, Nanopore Co.), S-C; extrusion support (pore size 0.1 lm, Ceracomb Co.), S-D; extrusion support (pore size 0.8 lm, Ceracomb Co.).

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As shown in Fig. 3, S-A and -B show uniform pore size distribution, whereas S-C and -D show bimodal pore size distribution and very large pores around 100 lm pore size which induce pin-holes and cracks. Fig. 3 also indicates that the porosities of S-C and -D are much larger than those of S-A and -B. Fig. 4 shows N2 permeances of four types of supports. Permeation mechanism of supports is viscous ow mechanism all together in which permeance increases as the feed pressure increases. S-A, -B, and -C supports show similar permeances but S-D shows higher permeance because it has non-uniform pore size distribution and very high porosity. Although S-C has high porosity and very large pore around 100 lm, it shows similar permeance to S-A and -B as shown in Fig. 4. Considering that pore size distribution is measured by mercury porosimeter, it can be explained that S-C has many closed-pores. Also thickness of S-C support is relatively very high. Therefore, large pores around 100 lm of S-C support cause bad eects on synthesis of the membrane. 3.2. Microstructure of ZSM-5 zeolite membrane ZSM-5 zeolite layers were hydrothermally grown on the surface of a-alumina support. The composition of
0.10

1E-4

N2 permeance (mol/m .s.Pa)

S-A S-B S-C S-D

1E-5

1E-6 1.0

1.5

2.0

2.5

3.0

3.5

4.0

Feed pressure (100 kPa)

Fig. 4. N2 permeances of a-Al2O3 supports.

the reaction mixture (mole ratio) was xSiO2:1.2NaOH:0.15TPAOH:0.15TPABr:140H2O. Based on the silica content, the value of (x) changes from 1 to 2.5, the formation of synthesized crystals and the separation factor of the membrane on S-C support are dierent as shown in Table 1. Fig. 5 shows the top surface SEM images of dierent crystal sizes, coverage, and intergrowths of the crystals synthesized on S-C support at
0.040

S-A

Incremental Intrusion (mL/g)

Porosity = 35 %

Incremental Intrusion (mL/g)

S-B
0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000 10 1 0.1

Porosity = 35.28 %

0.08

0.06

0.04

0.02

0.00 10 1 0.1 0.01 1E-3

0.01

1E-3

Pore diameter (m)

0.07

Pore diameter (m)

0.07

Incremental Intrusion (mL/g)

0.06 0.05 0.04 0.03 0.02 0.01 0.00 0.01

Incremental Intrusion (mL/g)

S-C

Porosity = 47.95 %

0.06 0.05 0.04 0.03 0.02 0.01 0.00 0.01

S-D

Porosity = 42.56 %

0.1

10

100

1000

Pore diameter (m)

0.1

10

100

1000

Pore diameter (m)

Fig. 3. Pore size distributions and porosities of a-Al2O3 supports.

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Table 1 Eects of the SiO2 content on formation of the zeolite layer on S-C support under hydrothermal conditions of 185 C and 40 h Sample no. Composition of reaction mixturea (mole ratio) Formation of ZSM-5 layer on support Size (lm) ZM12 ZM43 ZM52 ZM36 ZM55 ZM61
a b c b

CO2/N2 separation factor

c

Coverage Partial Full Full Full Partial Partial

Intergrowth Poor Bad Ok Good Bad Poor

1:1.2:0.15:0.15:140 1.5:1.2:0.15:0.15:140 1.75:1.2:0.15:0.15:140 2:1.2:0.15:0.15:140 2.25:1.2:0.15:0.15:140 2.5:1.2:0.15:0.15:140

30 30 3 3 8 8

1 1 1.5 5.7 3.1 1.4

Molar ratio SiO2:NaOH:TPAOH:TPABr:H2O. ZSM-5 crystal sizes estimated along c axis. Judged from the morphology of the top layer by SEM micrographs.

Fig. 5. SEM images of crystals synthesized on S-C support depending on the SiO2 content of reaction mixtures as per Table 1.

185 C for 40 h according to dierent SiO2 compositions as per Table 1. Fig. 6 shows the phases of covered crystals and supports. Although the peaks of a-alumina in the XRD patterns are more distinct than those of ZSM-5 zeolite because of the well-absorption feature of X-ray into a-alumina, ZSM-5 zeolite peaks are obvious when the appropriate starting composition is applied. Because the crystal size, coverage, and inter-

growth are not appropriate at reacting solution composition except for x = 2 about S-C support, crystals synthesized on S-C support do not show high separation factors. After considered the inuence of the silica content on the reacting solution, ZSM-5 zeolite membranes were synthesized on each support with a silica content of x = 2.25. Fig. 7 shows the top surface SEM images of

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319

ZSM-5 analcime -alumina

x = 2.5

x = 2.25 x=2 x = 1.75 x = 1.5

x=1 support
5 10 15 20 25 2 (degree) 30 35 40

Fig. 6. XRD patterns of lms prepared on S-C support using reaction mixtures of dierent SiO2 contents as per Table 1 (x = number of SiO2 moles).

dierent ZSM-5 zeolite membranes of four kinds of supports at x = 2.25 as per Table 2. Although the compositions of reacting solutions were the same, the formation and separation factors of synthesized membranes were dierent as shown in Fig. 7 and Table 2. The ZSM-5 zeolite membrane synthesized from the reaction mixture of x = 2.25 showed the appropriate

zeolite membrane layer which seemed to be defect-free and had the approximate thickness of 20 lm as shown in Figs. 7 and 8. Because the separation factor of the ZSM-5 zeolite membrane on S-B support is best as 28.1 at x = 2.25, we focused the synthesis on S-B support. In this work, the most eective ZSM-5 zeolite membranes could be obtained only from the extrusion support supplied by Nanopore Co. The operation time of hydrothermal treatment aects crystal shapes of the membrane supported a-alumina. For the short operation time, the small-sized seeds, which are crystallized to ZSM-5 zeolite crystals by the nucleation and growth mechanism at specic operation times, were formed from the reaction between the reacting solution and the initial leached Al content from the support. On the other hand, for the long operation time, the silicalite phase of roughly spherical shape on ZSM-5 phase is shown. The silicalite crystals on the ZSM-5 membrane probably impose a bad inuence on the separation eciency. The silicalite phase is formed by the very high Si/Al composition ratio when the Al leaching from a-alumina support is reduced during the very long hydrothermal treatment progress. Fig. 9 shows the top surface SEM image of the synthesized membrane which was surface-modied to improve separation eciency via lling up the intercrystalline voids among the zeolite crystals using the polymeric silica sol. The surface-modied membrane looks similar to the membrane before surface-modication. The polymeric silica gel blocks the intercrystalline voids eciently and covers the crystal surface very thinly.

Fig. 7. Top surface SEM images of dierent ZSM-5 zeolite membranes of four kinds of supports by the hydrothermal treatment conditions as per Table 2.

Arbitrary intensity

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Table 2 Eects of the support type on the CO2/N2 separation factor for the equi-molar CO2/N2 mixture at room temperature Support Composite membrane Composition of reaction mixturea (mole ratio) Hydrothermal conditions Temperature (C) S-A S-B S-C S-D
a b

CO2/N2 separation factorb 8.2 28.1 3.1 1

Time (h) 40

MSA MSB MSC MSD

2.25:1.2:0.15:0.15:140

185

Molar ratio SiO2:NaOH:TPAOH:TPABr:H2O. Stage cut (h) = 0.02, without helium sweeping.

Fig. 8. Cross section SEM images of the support (S-B) and the ZSM-5 zeolite membrane (MSB) synthesized by hydrothermally treating the reaction mixture of 2.25SiO2:1.2NaOH:0.15TPAOH:0.15TPABr:140H2O at 185 C for 40 h on S-B support as per Table 2.

Fig. 9. Top surface SEM images of the ZSM-5 zeolite membranes (a) before and (b) after surface-modifying by the polymeric silica sol; (a) MSB and (b) surface-modied MSB as per Table 2.

Consequently, the surface-modication decreased the gas permeance, while increased the CO2/N2 separation factor of the membrane. Sasaki et al. [25] reported on the microstructure analysis using TEM for a zeolite layer on a-alumina support. The actual zeolite crystal layer for gas separation is formed as a composite layer in the pores of the a-alumina support. Therefore, the shape of the top zeolite layer is not enough to estimate the eciency of the membrane performance. In summary, the separation performance of the zeolite membrane should not be characterized only by the top view of the SEM image of the zeolite layer crystals.

3.3. CO2/N2 permeance and separation factor The separation factor of the ZSM-5 zeolite membrane changes according to the stage cut (h) which means the ratio of the permeate ow rate to the retentate one. As the stage cut increases, the separation factor decreases exponentially as shown in Fig. 10 because the CO2 concentration in the feed side is aected by the retentate ow. That is, the higher the retentate ow is, the higher is the CO2 concentration in feed side, and the higher is the separation factor. Enhancement of the separation factor by He sweeping as shown in Fig. 11 is explained by the fact that

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29.5 29.0 28.5
1E-6 60

321

Permeance (mol/m .s.Pa)

Feed pressure = 400 kPa o Permeation temperature = 25 C No sweeping

Permeation temperature = 25 C Feed flow rate = 350 ml/min He sweeping rate = 100 ml/min CO2

Separation factor

28.0 27.5 27.0 26.5 26.0 25.5 0.0

S.F.

1E-8

50

1E-9

N2

1E-10 1.0

1.5

2.0

2.5

3.0

3.5

4.0

40

0.1

0.2

0.3

0.4

0.5

Feed pressure (100 kPa)

Stage cut ()
Fig. 10. CO2/N2 separation factor vs. stage cut (h) for surfacemodied ZSM-5 zeolite membrane.

Fig. 12. CO2/N2 permeance and separation factor vs. feed pressure for the surface-modied ZSM-5 zeolite membrane.

55 50

45 40 35 30 25

Feed pressure = 400 kPa o Permeation temperature = 25 C Feed flow rate = 350 ml/min

20

40

60

80

100

120

140

He sweeping rate (ml/min)

Fig. 11. CO2/N2 separation factor vs. helium sweeping rate for the surface-modied ZSM-5 zeolite membrane.

He sweeping increases the surface diusion rate of CO2 and decreases the permeate pressure (i.e. transmembrane pressure is increased by He sweeping). As shown in Fig. 12, the decreasing rate of N2 permeance according to the increase of feed pressure through the membrane is larger than that of CO2 in an equi-molar CO2/N2 gas mixture system, unlike other reports [2023,2629]. In the CO2/N2 mixture gas system, the CO2 ow mechanism is adsorption/surface diusion and micropore diusion, and N2 ow mechanism is micropore diusion of which the activation energy barrier is very high. Because the reported ZSM-5 zeolite , micropore diusion of N2 at channel size is about 6 A the core channel of zeolite pore is disturbed by the surface diusion layer of CO2 eciently in that channel size. Namely, CO2 adsorption on ZSM-5 zeolite pore wall increases when the feed pressure increases, and then the CO2 adsorption layer blocks N2 ow eciently in

the ZSM-5 zeolite channel. On the contrary, in the NaY zeolite membrane [1922], when CO2 adsorption increases on zeolite pore wall as the feed pressure increases, the inuence of increase of the N2 micropore diusion rate according to increase of the feed pressure on the separation factor is larger than the CO2 blocking eect to N2 ow. Because the reported NaY zeolite , the N2 micropore diusion channel size is about 7.5 A is not disturbed eectually by the surface diusion layer of CO2 in that channel size when the feed pressure increases. Therefore, as the feed pressure increases, the separation factor of NaY zeolite membrane decreases. Fig. 13 shows the CO2 and N2 permeances, and the CO2/N2 separation factor of the surface-modied ZSM-5 zeolite membrane synthesized on S-B support as a function of permeation temperature. As the permeation temperature increases, CO2/N2 separation factor decreases. It is explained that CO2 surface diusion rate on the zeolite pore wall increases to 100 C, but activated N2 micropore diusion increases more. In general, recent papers report that CO2 adsorption on the zeolite

Separation factor

1E-6

Feed pressure = 400 kPa Feed flow rate = 350 ml/min He sweeping rate = 100 ml/min

60 55

Permeance (mol/m .s.Pa)

1E-7

CO2

45 40

1E-8

35 30

1E-9

N2

25
S.F.

20 15

1E-10 20

30

40

50

60

70

80
o

90

100

10 110

Permeation temperature ( C)
Fig. 13. CO2/N2 permeance and separation factor vs. permeation temperature for the surface-modied ZSM-5 zeolite membrane.

Separation factor

50

Separation factor

1E-7

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Feed pressure = 400 kPa o Permeation temperature = 25 C Feed flow rate = 350 ml/min He sweeping rate = 100 ml/min

60 50

40 30 20 10 0 0 10 20 30 40 50 60

the CO2/N2 separation factor of 14.9 at 100 C in the equi-molar CO2/N2 gas mixture under separation conditions of feed pressure = 400 kPa, feed ow rate = 350 ml/min, and helium sweeping rate = 100 ml/ min. The moisture eect on CO2/N2 separation factor is negligible. The permeation of CO2 through ZSM-5 zeolite membranes was turned out to be mainly governed by both mechanisms of the adsorption/surface diusion and the activated micropore diusion, while that of N2 was governed by the activated micropore diusion only.

Separation factor

Test time (minute)

Fig. 14. CO2/N2 separation factor vs. gas permeation test time for the surface-modied ZSM-5 zeolite membrane in the moisture-saturated feed gas system.

Acknowledgement This research was supported by a grant (code # DA1203) from Carbon Dioxide Reduction & Sequestration Research Center, one of the 21st Century Frontier Programs funded by the Ministry of Science and Technology of Korean government.

pore wall increases until an appropriate temperature is reached but decreases at higher temperatures [1922]. As shown in Fig. 14, the separation factor of the ZSM-5 zeolite membrane in moisture-saturated feed gas system increases as the permeation test time increases. The separation factor of high value above 50 in dry feed gas system is decreased by inow of high humidity at the beginning and worst of all, permeate N2 ow is more than CO2 ow because CO2 adsorption on the zeolite pore wall is hindered by moisture. But as permeation test time increases, moisture occupies the large pores through which N2 ows mainly and as a result of that, CO2/N2 separation factor in moisture-saturated feed gas system is slightly higher than that in dry feed gas system. It is possible because ZSM-5 zeolite has a high hydrophobic quality.

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4. Conclusions ZSM-5 zeolite membranes supported with various aalumina tubes (slip-casted and extrusion supports of pore size 0.1 lm/0.8 lm) were synthesized by hydrothermal-treating support tubes in the reaction mixture of silica sol, sodium hydroxide, TPAOH, and TPABr at 185 C for 40 h in an autoclave. Formation of the ecient ZSM-5 zeolite layer on the support was found to be very sensitive to the surface morphology and the degree of Al ion leaching of a-alumina supports. The CO2/N2 separation factor of ZSM-5 zeolite membranes could be improved by minimizing the gas permeation through the intercrystalline voids via surface-modication by the dip-coating of the polymeric silica sol. Surface-modied ZSM-5 zeolite membranes showed the permeance of about 3.6 108 mol/m2 s Pa, the CO2/N2 separation factor of 54.3 at 25 C, and

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