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Separation and Purication Technology 59 (2008) 141150

Preparation of inner-side tubular zeolite NaA membranes in a continuous ow system

Marc Pera-Titus 1 , Marta Bausach 1 , Joan Llorens , Fidel Cunill
Chemical Engineering Department, University of Barcelona, 08028 Barcelona, Spain Received 21 February 2007; received in revised form 30 May 2007; accepted 31 May 2007

Abstract Zeolite NaA membranes were synthesized on the inner side of porous titania (rutile) asymmetric tubular supports in a ow system where the synthesis gel was circulated through the support with ow rates in the range 1.54 mL min1 by the action of gravity. The syntheses were carried out hydrothermally at 358 K for 67 h either with or without previous brush-seeding of the supports. The membranes (1020 m in thickness) showed great ability to dehydrate ethanol/water mixtures (92:8, w/w) by pervaporation with selectivities and uxes, respectively, up to 8500 and 1.2 kg m2 h1 at 323 K. The role of intercrystalline defects in the pervaporation performance of the synthesized membranes was also investigated. 2007 Elsevier B.V. All rights reserved.
Keywords: Zeolite membrane; Continuous synthesis; Pervaporation; Alcohol dehydration; Intercrystalline pathways

1. Introduction The research eld on zeolite membranes has gained increasing attention in the last two decades in both materials science and chemical engineering owing to their potential applications as membrane separators, catalytic membrane reactors, selective sensors and components in micro-electronic devices [15]. In particular, a great deal of studies have been devoted to the preparation of hydrophilic zeolite membranes for dehydrating azeotropic and close-boiling liquid mixtures by pervaporation [611]. Among these zeolites, zeolite NaA has been the target of many investigations due to its high Al/Si ratio and small pore size Under non-acidic conditions, zeolite NaA membranes (4.1 A). offer the double advantage of high selectivity towards water separation (>10,000) and high water uxes. These attributes make them attractive for dehydrating solvents at industrial level [12]. Among the different synthetic strategies reported in the literature for zeolite membrane synthesis [1319], zeolite NaA membranes have been conventionally prepared by hydrothermal synthesis onto a porous support in one or several batch

Corresponding author. Tel.: +34 934034872; fax: +34 934021291. E-mail addresses: marc.pera-titus@ircelyon.univ-lyon1.fr (M. Pera-Titus), jllorensl@ub.edu (J. Llorens). 1 Present address: Institut de Recherches sur la Catalyse et lEnvironnement de Lyon (IRCELYON), UMR5256, CNRS/Universit e Claude Bernard, Lyon 1, France. 1383-5866/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2007.05.038

cycles, either in situ or with a preliminary seeding step (i.e. secondary growth method). The seeding of the support helps improving the quality and reproducibility of the zeolite layers by decoupling the nucleation and crystal growth steps [20,21]. By carefully controlling the seed layer coating the support through the use of a convenient technique (e.g. cross-ow ltration [22] or vacuum seeding [23]), the synthesized membranes show an improved separation performance and a preferential crystalline orientation. Table 1 shows a detailed survey of the most relevant seeding and hydrothermal synthesis conditions together with the available lab-scale techniques for zeolite NaA membrane preparation. Regarding the methods presented in Table 1, most of the studies have been devoted to preparing zeolite lms on at supports or onto the outer surface of tubular supports. In the special case of inner-side tubular membranes, more suitable for developing full-size industrial modules, gel renewal constitutes an effective strategy to partially overcome nutrient depletion due to the restricted accessibility of the synthesis solution to the lumen of the support. We have recently reported the batch preparation of high quality inner-side zeolite NaA membranes on -alumina under a low-g centrifugal eld [26], which creates an axial ow that renews the synthesis solution in contact with the membrane. In order to reduce the number of synthesis cycles, we have also addressed the preparation of inner-side zeolite NaA membranes using a semi-continuous synthesis system [24]. This technique, earlier conceived by Pina et al. [25] for outer-side

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Nomenclature a A S i (0)
S Ew S Ew ,eff S Kw

M S Nw 0 Pw R SWG T xw Xw Yw

activity parameters in the Antoine equation for vapor saturation pressure (K1 ) MS surface diffusivity of water at zero coverage (m2 s1 ) activation energy of water diffusion (kJ mol1 ) effective activation energy of water diffusion dened by Eq. (2) (kJ mol1 ) adsorption constant of water (Pa1 ) thickness of the zeolite layer (m) molecular weight (kg mol1 ) surface ux of water (kg m2 s1 ) saturation vapor pressure of water (Pa) constant of gases (8.314 Pa m3 mol1 K1 ) seeding weight gain (mg cm2 ) temperature (K) molar fraction of water in the liquid feed weight fraction of water in the liquid feed weight fraction of water in the vapor permeate

side tubular zeolite membranes by inducing a forced ow have been reported in the literature. In this way, Richter et al. [34] have reported the synthesis of ZSM-5 membranes on the inner side of -alumina tubes and capillaries at 423 K for 72 h by pumping the synthesis gel in the lumen of the supports at a ow rate in the range 414 mL min1 (0.25 cm min1 ). Culfaz et al. [35] have also prepared good quality MFI-type zeolite membranes on alumina tubular supports at 355368 K for 7276 h in one to three cycles with a circulation of the synthesis gel by the action of a peristaltic pump at a ow rate of 648 mL min1 . To our knowledge, the use of a ow system for zeolite NaA membrane synthesis has only been reported by Yamazaki and Tsutsumi [36] on at supports, but has not already been reported for inner-side tubular congurations. Accordingly, this study is aimed at the hydrothermal synthesis of inner-side zeolite NaA membranes in a continuous ow system where the synthesis gel is own by the action of gravity. The technique is promising for scaling up the synthesis process and for zeolite NaA synthesis in multi-channel tubes and capillaries. 2. Experimental The zeolite NaA membranes were prepared by in situ and seeded hydrothermal synthesis on the inner-side of tubular asymmetric supports of 8 mm i.d. and 10 mm o.d. (TAMI, France). At the innermost part of these supports there was a 0.8 m poresize titania (rutile) layer of approximately 40 m in thickness. Before the synthesis, the tubes were subjected to enameling at both ends with a commercial glaze (Duncan AN 313 Antique Blue) and a home-made glaze, both resistant to strong alkali, leaving an effective permeation length of approximately 5 cm and inner area of 12.6 cm2 . The glazed tubes were dried at room temperature for a few minutes and then heated to 1173 K for 15 min with a heating ramp of 1 K min1 . 2.1. Seeding of the supports Prior to secondary growth synthesis, the inner surface of the tubular supports was brush-seeded with A-type zeolite crystals (2 m) supplied by IQE (Industrias Qu micas del Ebro, Zaragoza, Spain). To this end, zeolite NaA crystals were powdered on a thin test-tube brush capable of penetrating the lumen of the supports. Then the inner side of the supports was seeded by rotating the zeolite-loaded brush along the tube axis. The zeolite layer coating the support after the seeding was measured in terms of seeding weight gain (SWG) [mg of seeds cm2 of surface area]. 2.2. Hydrothermal syntheses The hydrothermal syntheses were carried out in one cycle for periods of 37 h at atmospheric pressure in the temperature range 353363 K with a cloudy synthesis gel of molar composition 1.0 Al2 O3 :1.8 SiO2 :3.9 Na2 O:270 H2 O. The gel was prepared using two aluminate and silicate precursor solutions according to the procedure reported previously [22]. The aluminate solution was prepared by dissolving the appropri-

Greek symbols 0 Hw adsorption enthalpy of water on zeolite NaA (kJ mol1 ) density of zeolite NaA (1900 kg m3 ) S

zeolite NaA membrane synthesis, allows pulse-renewal of the synthesis solution in an autoclave at periodic intervals by the action of a set of electro-pneumatic valves. Layer formation can be controlled by adjusting the gel renewal rate (i.e. the rate at which fresh gel is introduced into and used gel removed out of the autoclave). The membranes with the best pervaporation performance are those prepared with gel renewal rates lying in the range 1/41/7 min1 (i.e. introduction of fresh gel every 47 min). These membranes give selectivities and uxes up to 16,000 and 0.6 kg m2 h1 , respectively, for the separation of 92:8 (w/w) ethanol/water mixtures at 323 K. Despite the benets of the semi-continuous synthesis system in terms of layer growth control, this technique presents some drawbacks regarding large-scale implementation. First, it involves the synthesis of membranes in an autoclave lled with a volume of 155 mL of synthesis gel that surrounds the tube (95% of total volume), but which itself is not employed in the synthesis of inner-side layers, thus contributing negatively to the economy of the process. A second shortcoming is related to the periodical pulse-renewal of the gel in the lumen of the support, which might sweep away the zeolite seeds and remove the amorphous gel layer covering the support surface during the synthesis. Finally, two semi-continuous synthesis cycles are often required to ensure good PV performance. To overcome all the above stated limitations, an alternative method for gel renewal can focus on using a ow system where the gel is continuously circulated in the lumen of the tubes. However, only a few studies dealing with the synthesis of inner-

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References

143

[24]

[25]

[22]

[26]

[22] [27] [28] [29] [30] [9]

Seed size (m)

[8]

0.33.0 1 1 1

2, 4

200 mesh

NA NA Rubbing Rubbing

[31] [32]

Brush seeding; C-F ltration

C-F ltration Dip coating UV (32 W) Dip coating

Rubbing; Dip coating

Brush seeding

C-F ltration

Rubbing

Rubbing; Dip coating

Seeding technique

0.7

[33]

[6]

Fig. 1. Scheme of the continuous ow system used for inner-side zeolite NaA membrane synthesis.
-Al2 O3 outer tube Hollow ber -Al2 O3 disk TiO2 disk -Al2 O3 disk Mullite, -Al2 O3 outer tubes

Table 1 Conditions for zeolite NaA membrane preparation by hydrothermal synthesis

Notation: Autoclave (AC); vessel open to atmosphere (VS).

ate amount of sodium aluminate powder supplied by Aldrich (Al2 O3 = 53 wt.%, Na2 O = 43 wt.%, Fe2 O3 = 4 wt.%) in deionized water at 343 K under vigorous stirring in a closed ask. The silicate solution was prepared by dissolving a sodium silicate solution supplied by Aldrich (SiO2 = 27 wt.%, NaOH = 14 wt.%) in the remaining water under stirring. The silicate solution was added in three consecutive steps to the aluminate solution under vigorous stirring and the temperature was kept to 343 K. The scheme of the experimental set-up used for inner-side zeolite NaA membrane synthesis is depicted in Fig. 1. In general terms, the support, with the outer surface wrapped with Teon tape to avoid crystal deposition, was placed inside a module immersed in a temperature-controlled oil bath. The gel was own through the lumen of the tube by the action of gravity from a reservoir (2 L) preheated at 323 K and kept under mild stirring to a discharge vessel. A thermocouple positioned in the lumen of the tube was used to monitor any temperature uctuation with gel introduction. In this work, the gel ow rate was xed at a value in the range 1.54 mL min1 for all the synthesized membranes, which is expected not to sweep away the growing zeolite layer on the support inner surface. The gel ow rate could be regulated by means of the height difference between the level of the gel in the reservoir and that at the outlet of the system. The height difference was progressively increased from an initial value of 10 cm, in the beginning of the synthesis to compensate the reduction of the gel level in the reservoir. At the end of the synthesis, the as-synthesized membranes were removed from the module, washed with boiling water for 1 h and dried in an oven at 373 overnight under vacuum (<103 mbar). 2.3. Membrane characterization The as-synthesized membranes were rst characterized in terms of weight gain [mg cm2 ] and N2 permeance at room temperature to evaluate, respectively, the amount of zeolite material grown onto the support and the presence of large defects in the

-Al2 O3 inner tube

-Al2 O3 outer tube

-Al2 O3 inner tube

-Al2 O3 inner tube

-Al2 O3 outer tube

-Al2 O3 disk 540 min/1 15 min/1 363 363 Static (VS-MW 2450 MHz) 1:2:3:200 1:5:50:1000

Time (h)/cycles

24/1 24/1 1624/13 4/1 16/1 3.5/1

5/12

3/24

3/23

36/1

48/1

5/1

T (K)

363373

363373

353373

323

Composition of the synthesis solution (Al2 O3 :SiO2 :Na2 O:H2 O: templates)

363

1:5:50:1000 1:2:3:200 1:2:3:200 1:4.4:41.9:833.3 1:5:50:1000 1:2:2:120

1:2:2:120400

1:5:55.1:1004.7

333 363 363 353 363 373

373

1:1.8:3.9:273

1:1.8:3.9:273

1:1.8:3.6:270

1:2:2:80144

Semi-continuous (AC) (1/41/16 min1 ) Semi-continuous (AC) (1/131/25 min1 ) Centrifugal eld (VS) (100 rpm) Centrifugal eld (VS) (5202520 rpm) Dynamic (AC) (75 rpm)

Reactor conguration

Static (VS with distiller)

Static (VS)

Static (AC)

1:9:80:5000

353

5/1

-Al2 O3 disk

Support

ZrO2 /C sheet

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zeolite layer. The dehydration performance of the as-synthesized membranes was rst studied by vacuum PV for the separation of a 92:8 (w/w) ethanol/water mixture at 323 K with the permeate pressure kept <2 mbar. The set-up used to carry out the PV tests is described elsewhere [22,24]. In addition, to survey the effect of large defects in the PV performance, some PV tests were also done for the dehydration of short- and long-chain primary alcohols. Care was taken in the experiments carried out with C4 and C5 alcohols (i.e. 1-butanol and 1-pentanol) to ensure miscibility of their liquid mixtures with water. The water/alcohol selectivity of the membranes was calculated as the quotient between the ratios of the weight fractions of water and alcohol at the permeate and feed sides, i.e. w/A = (Yw /YA )/(Xw /XA ). The composition in the feed and permeate were analyzed in a HP6980A GC equipped with a 50 cm 0.2 mm 0.5 mm methyl silicone capillary column and a TCD detector. The nal values correspond to the mean of at least two consecutive steady-state measurements taken after 3 h of stabilization. The standard deviation of the total ux and selectivity was found to be <5 and <10%, respectively, for all the experiments. The structure of the phases obtained after synthesis was characterized by X-ray diffraction (XRD) analysis (Cu K radiation, Siemens D-500), while the morphology of the membranes was inspected by scanning electron microscopy (SEM), operating at 15 kV (Hitachi S-2300). 3. Results and discussion

Furthermore, the lowest values of N2 permeance for the membranes prepared in a ow system fall into the range 6 to 10 109 mol m2 s1 Pa1 , which is ca. four orders of magnitude lower than the permeance of a fresh support. It should be noted that this range is very similar to that found for both outerand inner-side tubular zeolite NaA membranes synthesized in the semi-continuous system. This result reinforces the idea that gel renewal helps improving the quality of inner-side zeolite NaA layers. However, in the case of the membranes synthesized in the continuous ow system, higher layer intergrowth and thus lower number of meso- and macroporous defects in the zeolite layer is obtained at lower weight gain values after synthesis. This suggests that this technique is more efcient than the semicontinuous synthesis system for inner-side membrane synthesis. Contrary to what is observed when preparing membranes under a centrifugal eld or in the semi-continuous system, a no clear trend is observed between the weight gain after synthesis and the SWG. Nevertheless, as expected, the membranes synthesized with a previous brush-seeding at a SWG in the range 0.110.27 mg cm2 show lower N2 permeances. It should be highlighted that this interval compares well with that found when using the semi-continuous synthesis system with a preliminary brush-seeding step (0.110.20 mg cm2 ) [24] and corresponds approximately to the weight of a monolayer of seeds (for 2 m seeds and a zeolite density of 1.9 g cm3 the weight of a monolayer of seeds would be 0.25 mg cm2 , assuming avoid fraction of 0.3 in the monolayer). 3.2. Characterization by XRD and SEM analyses

3.1. Weight gain and N2 permeance Table 2 lists the synthesis conditions together with the main results concerning the weight gain and N2 permeance of the assynthesized membranes prepared in this work. As can be seen, the weight gain of the membranes synthesized for 7 h with a previous bush-seeding lies in the range 3.58.5 mg cm2 , which is somewhat lower than that obtained for inner-side membranes synthesized on -alumina supports in a semi-continuous system with the same gel in one cycle of 5 h, 520 mg cm2 [24]. This difference in weight gains between both techniques might be ascribed to the lower temperature range at which the continuous system operates, 353363 K, compared to that of the semi-continuous system, 363373 K. Fig. 2 shows the XRD patterns of the inner-side zeolite NaA membranes ZA2, ZA4 and ZA07 prepared in the continuous ow system. For all these membranes, pure zeolite NaA was the only zeolitic phase present on the support. The peaks corresponding to the rutile layer can also be observed and are marked with an asterisk in the gure. As can be seen, the intensity of the peaks related to membranes ZA04 and ZA07 is higher than that of membrane ZA02, while that related to peaks corresponding to the rutile layer are less intense for the former two membranes. These observations might be ascribed to the larger zeolite layer thickness of membranes ZA04 and ZA07, since they have been synthesized at longer synthesis times (67 h versus 3 h). On the other hand, the XRD pattern of membrane ZA04 prepared by the

Table 2 Synthesis conditions, weight gain after synthesis and N2 permeance of the membranes prepared in the continuous ow system (T = 353363 K, gel ow rate = 1.54 mL min1 ) Membrane ZA01 ZA02 ZA03 ZA04 ZA05 ZA06 ZA07 ZA08 ZA09 Time (h) 3 3 7 7 7 7 6 7 7 SWG (mg cm2 ) 0.21 0.13 0.27 0.11 0.12 0.00 0.00 0.00 0.00 Weight gain (mg cm2 ) 3.63 8.22 9.19 4.70 8.53 3.51 5.86 7.24 6.35 N2 permeance (mol m2 s1 Pa1 ) 2.05 107 3.70 108 6.09 108 4.45 107 1.68 109 1.00 105 2.24 106 2.04 108 5.12 108

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145

Table 3 PV performance of the membranes prepared in the continuous ow system in comparison with those reported in our previous literature Membrane Synthesis technique PV resultsa Selectivity (W/E) ZA01 ZA03 ZA04 ZA05 ZA08 ZA09 ZA10b ZA11b ZA12c ZA13c ZA14 Fig. 2. XRD patterns of zeolite NaA layers grown onto the inner surface of seeded and unseeded tubular supports (T = 358 K; synthesis time = 67 h; gel ow rate = 1.54 mL min1 ). (a) Membrane ZA02, SWG = 0.11 mg cm2 ; (b) membrane ZA04, SWG = 0.13 mg cm2 ; (c) membrane ZA07, SWG = 0 mg cm2 . The asterisk shows the location of rutile peaks from the support.
a

NT (kg m2 h1 ) 0.93 0.76 1.16 0.89 0.72 0.97 0.48 0.48 0.62 0.32 >1.50

Continuous ow system

51 1091 495 8538 160 76 2444 1050 502 294 <10

Semi-continuous system Centrifugal eld Batch synthesis

PV conditions: feed pressure, 13 bar; feed water fraction, 89 wt.%; T, 323 K; permeate pressure, 13 mbar. b From ref. [15]renewal rate: (at a) 1/7 min1 ; (at b) 1/4 min1 ; (at c) two synthesis cycles; -Al2 O3 support. c From ref. [17]rotational speed, 100 rpm; (at c) three synthesis cycles; -Al2 O3 support.

secondary growth method shows higher and more denite peaks than that of membrane ZA07 prepared by in situ hydrothermal synthesis. Accordingly, the seeding of the support appears to provide more crystalline layers due to a more uniform and controlled growth of the zeolitic material. Fig. 3 shows some SEM micrographs of membranes ZA02, ZA04 and ZA07. The inspection of the top view micrographs of these membranes (see Fig. 3a1c1) reveals in all cases the presence of well-intergrown layers constituted by a randomly oriented distribution of cubic and truncated-side cubic crystals. In good keeping with the XRD patterns plotted in Fig. 2, the differences in surface morphology observed for membrane ZA07 (Fig. 3a1) compared to membranes ZA02 and ZA04 (Fig. 3a1b1) might be attributed to the presence of amorphous material on the layer. Fig. 3a2c2 show that the membranes consist of three layers: (1) synthesized zeolite layer, (2) intermediate titania layer and (3) bulk support constituted by large crystals that generates a macroporous array of 7 m mean pore size. In all cases, the thickness of the zeolite layer lies in the range 1020 m and increases with the synthesis time. The seeding of the support does not seem to exert an effect on layer thickness, in agreement to what is observed when preparing membranes in the semi-continuous system. 3.3. PV performance of the as-synthesized membranes The results of the PV tests carried out on the as-synthesized membranes towards the dehydration of ethanol/water mixtures are summarized in Table 3. For comparison, Table 3 also includes some reported data concerning the PV performance of some membranes synthesized under a centrifugal eld and in a semicontinuous system. As can be seen, in the optimal synthesis conditions, a continuous ow system provides membranes with excellent selectivities and high total uxes. A stability test car-

ried out for membrane ZA05 (see Fig. 4) reveals that this membrane preserves its PV performance for at least 100 h of continuous operation. It should be noted that the uxes for the membranes prepared in this work are ca. twice the value that can be obtained for membranes synthesized under a centrifugal force eld and in a semi-continuous synthesis system (see Table 3). This result is consistent with the reduction up to half of the layer thickness for the membranes prepared in a continuous ow system compared to those prepared with the other two aforementioned techniques. In addition, these uxes are as high as the best values reported in the literature for the PV separation of ethanol/water mixtures using both at and inner-/outer-side zeolite NaA membranes at the same temperature and feed composition (see Table 4 for comparison) and are comparable with those that can be obtained with commercial zeolite NaA membranes [41,42]. Fig. 5 shows a correlation between the N2 permeance and both the total ux and water/ethanol selectivity for the membranes listed in Table 2. As expected, the water/ethanol selectivity is reduced with the N2 permeance, while the total ux across the membrane shows the opposite trend. The membranes are only able to separate ethanol/water mixtures efciently when their N2 permeance is <3 108 mol m2 s1 Pa1 , which ensures a sufciently low concentration of meso- and macroporous defects in the zeolite layers to prevent them from a high contribution of non-separative viscous pathways to mass transfer. When comparing the results obtained in this work for innerside zeolite NaA membranes with those reported on previous works [22,24], it is interesting to note that the required loading of zeolite material to prepare membranes with good PV performance is nearly half of the value needed in the semicontinuous synthesis system operated at high renewal rates (i.e. 1/71/4 min1 ). At these renewal rates, the presence of a high

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Fig. 3. SEM micrographs of tri-layered membranes ZA02, ZA04 and ZA07 grown on asymmetric TiO2 supports. Top views, a1c1; cross-sections, a2c2. Synthesis conditions as in Fig. 2.

number of gel pulses in the lumen of the support using the semicontinuous system seems to make it more difcult to prevent the membranes from defect formation, thus requiring thicker layers to achieve a similar PV performance. 3.4. Effect of feed composition and temperature on the PV performance: role of intercrystalline domains Fig. 6 plots the effect of the feed composition on the total ux and water/ethanol selectivity at low feed water fractions

(210 wt.%) for membrane ZA05 prepared in a continuous ow system and for membranes ZA11ZA13 prepared using either a semi-continuous synthesis system or in the presence of a centrifugal eld (see Table 3). As can be seen in Fig. 6a, the total ux shows a linear increase with the water composition or water activity in the feed for all the membranes, as expected on the basis of the strong hydrophilic character of zeolite NaA. Given the trends shown in Fig. 6a, the surface diffusivities of water at zero coverage can be calculated using an adsorptiondiffusion model based on the MaxwellStefan diffusion theory as was

M. Pera-Titus et al. / Separation and Purication Technology 59 (2008) 141150 Table 4 PV performance of zeolite NaA membranes towards dehydration of ethanol/water mixtures Thickness (m) 1020 30 2030 10 7 NA 3.5 10 30 4 NA 30 5 7 10 56 Support TiO2 tube (i) -Al2 O3 tube (i) -Al2 O3 tube (i) -Al2 O3 tube (o) -Al2 O3 tube (i) ZrO2 /C sheet TiO2 disk Mullite tube (o) -Al2 O3 tube (o) -Al2 O3 disk Mullite tube (o) Mullite tube (o) SS tube (o) -Al2 O3 disk -Al2 O3 disk -Al2 O3 tube (i) Water in feed (wt.%) 10 8 8 10 9 10 5 10 10 10 5 10 10 10 10 5 T (K) 323 323 323 398 366 323343 318 323 323 303 298 333 313 298 333 323 Selectivity (W/E) 8500 600 >10000 3600 130 9001000 >10000 >10000 1700 10000 >10000 1000 180 3000 >10000 >10000 Flux (kg m2 h1 ) 0.81.0 0.50 0.50 3.80 2.50 0.160.18 0.86 0.77 0.79 1.00 0.68 1.20 0.079 0.072 0.57 1.50

147

Reference This study [22] [24] [25] [26] [8] [29] [9] [6] [33] [37] [7] [38] [39] [19] [40]

Notation: Outer tube (o); inner tube (i); not available (NA).
S . In the considered for the adsorption constant of water, Kw present calculations, the contribution of the support to the overall mass transfer has been omitted, since it has been found to be <5% for all the membranes. Irrespective of the synthesis method, the computed values of water surface diffusivities for all the tested membranes show the same order of magnitude, 1011 m2 s1 , in quite good agreement with that reported in our earlier study [43]. This observation reects that, although the total ux increases more abruptly with the feed water fraction in the case of membrane ZA05 than for membranes ZA11ZA13, this difference should be in principle attributed to the lower layer thickness of the former membrane (10 m versus 2030 m as determined by SEM, see Table 3). On the other hand, while the water/ethanol selectivity remains practically constant with the water composition in the feed for membranes ZA11ZA13, a positive trend is observed for membrane ZA05 (see Fig. 6b). Note that this trend is in good keeping with that observed by Okamoto et al. [6] and Shah et al. [7] at low water fractions for good quality at and outer-side tubular zeolite NaA membranes, respectively. Therefore, the difference in both trends might be in principle attributed to the presence of a higher number of large intercrystalline defects in the zeolite layers for the former membranes, which seems evident on

Fig. 4. Water/EtOH (W/E), selectivity () and ux ( ) as a function of time for membrane ZA05. PV conditions as in Table 3.

outlined in a previous work [43] S w (0) =

SY NT w ZA Sa 0 S qM Mw Kw w,L Pw

(1)

where the activity coefcients have been estimated by the UNIFAC method [44] and a value of 104 Pa1 has been

Fig. 5. Evolution of water/ethanol selectivity and total ux with N2 permeance. Pervaporation conditions as in Table 3.

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Fig. 6. Evolution of (a) total ux and (b) water/ethanol selectivity with water feed composition for membranes: (a) ZA5 (), (b) ZA11 ( ), (c) ZA12 ( ) and (d) ZA13 ( ). PV conditions as in Table 3. The straight and dashed lines refer to the trends observed for membrane ZA5 and for the set of membranes ZA11ZA13, respectively.

the basis of their lower water/ethanol selectivities compared to those of membrane ZA05. Fig. 7 shows the effect of temperature on the water ux and selectivity for the set of membranes ZA03, ZA05, ZA11 and ZA12. As expected, an Arrhenius trend of the water ux with temperature is observed for all the tested membranes (see Fig. 7a), with effective activation energies lying in the range 3340 kJ mol1 . These values agree, within the limits of the experimental error, with those reported by Kondo et al. [9] (see Table 5). Taking into account all the contributions to water mass transfer in the PV process according to an adsorptiondiffusion model [43], the effective activation energy of water includes the following contributions:
S S Ew ,eff = Ew + Ew Hw + RA

(2)

where is the activation energy for water surface diffusion, the adsorption enthalpy of water on zeolite NaA and Hw parameter A belongs to the Antoine equation that accounts for the evolution of saturation vapor pressure with the temperature (A = 5300 K1 for water in the temperature range 293363 K). Taking a value of 43 kJ mol1 for the adsorption enthalpy of water [43], the computed activation energy of water found in this study approaches the effective activation energy val = 43 kJ mol1 !!). ues (note that RA = 44.06 kJ mol1 Hw Therefore, the activation energy of water diffusion falls into the interval 3340 kJ mol1 , which compares well with the value

reported by Zhu et al. [45] from the separation of water/N2 mixtures using zeolite NaA membranes. Regarding the evolution of the water/ethanol selectivity with the temperature at low water fractions and in the temperature range 303363 K (see Fig. 7b), a maximum appears to be observed at 325 K for the best quality membranes, namely membranes ZA03 and ZA05 prepared in the continuous ow system. However, for membranes ZA11 and ZA13, a positive trend of the selectivity with the temperature seems to be observed. In agreement with the above stated considerations dealing with the role of intercrystalline domains, the discrepancy between both trends might be ascribed to the higher contribution of large defects in the latter membranes. For these membranes, when operated at low feed water fractions, a temperature raise might enhance water diffusion across the zeolite layer, thus compensating to a certain extent the preferential mass transfer of ethanol through large defects and therefore giving rise to an increase in the membrane selectivity. More insight into the effect of large intercrystalline pores in the PV performance in zeolite NaA membranes can be gained by comparing their ability towards dehydration of short- and long-chain primary alcohols. Fig. 8 plots the evolution of the total ux and selectivity towards water separation of membrane ZA13 with the length of chain of the primary alcohol in the liquid mixture at low water fractions (2.5 and 4.5 mol%) and at 323 K. As can be seen, while the total ux appears to be only

Fig. 7. Evolution of (a) total ux and (b) water/ethanol selectivity with temperature for membranes: (a) ZA3 (), (c) ZA5 ( ), (b) ZA11 ( ) and (d) ZA13 ( ). PV conditions as in Table 3. The straight and dashed lines refer to the trends observed for membranes ZA3 and ZA5 and for membranes ZA11ZA13, respectively.

M. Pera-Titus et al. / Separation and Purication Technology 59 (2008) 141150 Table 5 Effective activation energies of water ux across zeolite NaA membranes Membrane ZA03 ZA05 ZA11 ZA13 Zeolite NaA (outer-side) Zeolite NaA (at)
a

149

Synthesis technique Continuous ow system Semi-continuous Centrifugal eld Static batch Static batch

Xw range (wt.%) 4.34.7 3.94.2 2.559.0 4.85.2 10100 10

T range (K)

Ew,eff (kJ mol1 )a 34 1 39 2 40 4 33 3 35 5152

Reference This study This study This study This study [9] [7]

303363

313353

Typical error for a probability level of 95%.

Fig. 8. Evolution of (a) total ux and (b) water/alcohol selectivity with the number of carbon atoms in the alcohol for membrane ZA13. Feed composition: ( ) xw = 2.5 mol% and ( ) xw = 4.5 mol%. Other PV conditions as in Table 4. The straight lines refer to the trends observed.

slightly affected by the length of chain of the alcohol, except for methanol, whose molecule ressembles more to that of water, the selectivity becomes strongly promoted. As has been outlined by Okamoto et al. [6] when studying the performance of zeolite NaA membranes towards the dehydration of methanol, ethanol, acetone and DMF mixtures, the selectivity of the membranes is promoted as the ability of the solvent to adsorb on zeolite NaA is reduced. Moreover, despite the presence of a certain number of large defects in the zeolite layer, their contribution to mass transfer is compensated by that within zeolite pores due to their stronger hydrophilic character, which favors the adsorption of smaller molecules. 4. Conclusions A continuous ow system has been presented in this work that allows the synthesis of good quality zeolite NaA membranes on the inner-side of tubular ceramic supports. Compared to other reported methods for inner-side zeolite NaA membrane synthesis (i.e. semi-continuous and centrifugal force eld), this technique is economically advantageous, since only the gel lling the lumen of the support is refreshed along the synthesis. Taking into account that this technique can be easy to scaled-up, it constitutes a promising option for inner-side zeolite membrane synthesis at large scale and for zeolite NaA synthesis in multichannel tubes and capillaries. The selectivities and uxes of the membranes prepared using this technique approach the best values reported in the literature for inner-side zeolite NaA membranes. This latter aspect is especially promising in terms of membrane area economy. Notwithstanding the presence of a large number of defects, zeolite NaA membranes can be used

condently in PV applications that involve dehydration of heavy non-adsorbing species, like 1-butanol and 1-pentanol. Acknowledgements The authors would like to express their gratitude to the Spanish Ministry of Education and Science for nancial support (projects PPQ2000-0467-P4-02 and CTQ2005-08346-C02-01). The comments of Dr. Sylvain Miachon have been very useful in the preparation of this paper. References
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