Journal of Membrane Science 244 (2004) 141–150

A semi-continuous method for the synthesis of NaA zeolite

membranes on tubular supports
M.P. Pina, M. Arruebo, M. Felipe, F. Fleta, M.P. Bernal,
J. Coronas, M. Menéndez, J. Santamarı́a∗
Department of Chemical Engineering, University of Zaragoza, 50009 Zaragoza, Spain

Received 26 March 2004; received in revised form 23 June 2004; accepted 25 June 2004
Available online 11 September 2004

Abstract

Zeolite NaA membranes have been synthesized by secondary growth on the external surface of ␣-alumina tubular supports using a semi-
continuous system in which fresh gel was periodically supplied to the synthesis vessel. Compared to traditional batch methods, the procedure
developed in this work provides a better control of the synthesis and crystallization conditions and is easier to implement at an industrial scale.
The influence of the renewal rate during synthesis on the pervaporation and vapor permeation performance of the membranes was studied,
with the best performance corresponding to the case where the gel was renewed every 20 min of synthesis time. The membranes obtained by
the semi-continuous method displayed an excellent separation performance in the pervaporation of ethanol/water mixtures (e.g., a separation
factor of 3600 at a water permeation flux of 3.8 kg/h m2 ).
© 2004 Elsevier B.V. All rights reserved.

Keywords: Zeolite NaA membranes; Semi-continuous synthesis; Renewal rate; Pervaporation; Ethanol dehydration

1. Introduction able membrane. Recently, many investigations have reported

Supported zeolite membranes have been extensively
developed during the last decade in view of their poten-
tial applications in membrane separators, membrane reac-
tors and selective sensors [1,2]. Zeolite membranes combine
the intrinsic properties of zeolites and the advantages of a
membrane-type configuration, making them excellent can-
didates for the separation applications based on preferential
adsorption, differences in diffusion rates or molecular sieving
effects.
Pervaporation (PV) processes have been advocated as an
effective and energy-efficient technique for the separation of
azeotropic and close-boiling liquid mixtures, and for the de-
hydration of organic solvents [3]. On the other hand, vapor
permeation (VP) is a separation process in which the compo-
nents of a vapor-phase feed are selectively separated on a suit-
∗ Corresponding author. Tel.: +34 976 761153; fax: +34 976 762142.
E-mail address: iqcatal@posta.unizar.es (J. Santamarı́a).
on the PV properties of microporous inorganic membranes
including silica [4] and hydrophilic zeolite membranes such
as zeolite A [5–10], faujasite-type zeolites (X and Y) [11],
MFI-type zeolites [12] and mordenite [13]. It is clear that
zeolite membranes are interesting for industrial separation
processes on account of their chemical and thermal stabil-
ity, and of their highly specific interactions with permeating
molecules. However, the problem of reproducibly achieving
large membrane areas in suitable modules is still far from
fully solved, and this is likely one of the main reasons for
the much wider industrial development of non-zeolitic in-
organic membranes. Thus, at least several dozen industrial
manufacturers nowadays prepare a wide variety of inorganic
membranes (glass, silica, metallic, ceramic and carbon [14]),
while only one type of zeolite membrane (zeolite A) is indus-
trially manufactured on a relatively large scale, and by one
company (Mitsui Engineering).
A survey of recent literature on zeolite membrane prepa-
ration reveals that synthesis processes, even for well-known

0376-7388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2004.06.049
142 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150
zeolite structures (e.g., MFI, LTA) are still carried out batch-
wise, using a hydrothermal route. Successful membrane for-
mation in one-process (direct membrane synthesis) requires
nucleation and growth of zeolite crystals on the support sur-
face, a process that competes with solution events. To reduce
crystal nucleation and growth in the bulk of the synthesis solu-
tion the so-called secondary (seeded) growth methods can be
used, involving a first step in which a closely packed layer of
zeolite seed crystals is deposited onto the surface of a support.
In this way, subsequent hydrothermal synthesis can be car-
ried out under less concentrated conditions that are sufficient
for crystal growth but hinder nucleation in the bulk. Both di-
rect and secondary synthesis methods may be acceptable for
small-scale applications (a few cm2 of membrane area), but
present significant problems of the synthesis of larger struc-
tures. Generally speaking, increasing the zeolite membrane
area in industrial modules involves the use of longer tubu-
lar or monolith supports, and/or reduction of tubular diame-
ters to capillary dimensions to increase the membrane area
per unit volume. In addition to the variations of composition
with time that necessarily take place during batch process-
ing, the use of longer and narrower supports will likely cause
the development of concentration gradients, leading to non-
homogeneous membrane characteristics, and possibly also
to the formation of defects and non-desired phases on the
membrane.
A number of studies have attempted to solve the prob-
lems that prevent the synthesis of large area membranes.
Regarding hydrothermal synthesis, the works of Morigami
et al. [9] and Li et al. [15], who prepared NaA zeolite and
ZSM-5 zeolite membranes, respectively, on tubular alumina
supports are noteworthy, since the surface of the membranes
prepared approached 300 cm2 per tube. Although batch pro-
cessing was used in both cases, successful membrane forma-
tion was achieved either by using a suitable excess of reactants
[9] or by repeated synthesis cycles [15]. Another possibility
that could be explored to circumvent the problem of reactant
depletion during synthesis is the use of the so-called dry gel
method, involving deposition of a layer of dry aluminosil-
icate gel on the support, followed by the transformation to
the zeolite under the presence of vapors [16]. Other authors
propose the direct heating of the substrate while the reaction
mixture is kept at lower temperature [17,18]. In this manner,
the reaction is suppressed in the bulk and promoted on the sur-
face, and the phase transformations of metastable materials
to other zeolite types (P zeolite, X zeolite, hydroxi-sodalite)
can be delayed.
Even if the problems of reactant depletion and synthesis of
zeolite material in the bulk of the solution were solved, an im-
portant problem remains, related to the fact that several batch
synthesis cycles (with their associated heating and cooling
processes) are often required to achieve a zeolite membrane
of good quality. Thus, a synthesis procedure in which reac-
tants are continuously supplied to the synthesis vessel while
this is maintained at a constant temperature would clearly
be desirable. Yamazaki and Tsutsumi [19] prepared A-type
zeolite flat membranes on PTFE and glass supports using
a circulated solution system 50 cm3 /min and heating only
the substrate area in the range of 353–403 K for crystallisa-
tion periods of 24–48 h. Under these conditions, the forma-
tion of phases concomitant to NaA zeolite was avoided and
the amount of crystals forming in the liquid phase could be
greatly reduced. Kumakiri [20] proposed a continuous sys-
tem for cross-flow filtration of a suspension of zeolite A not
only for the formation of a seed layer but also for the subse-
quent membrane growth under a constant feed flow rate. The
tubular zeolite membranes obtained showed modest pervapo-
ration selectivity, with H2 O/ethanol separation factors of 25
for a zeolite layer thickness of 2 ␮m. The author pointed out
that the use of longer synthesis times should make the zeolite
membrane denser and increase selectivity. Richter et al. [21]
have prepared 30 ␮m thick ZSM-5 membranes on the inner
surface of ceramic tubes and capillaries by seeding with nano-
sized MFI particles and pumping a clear synthesis solution
0.25 cm/min through the support tubes. The membranes so
obtained showed H2 /SF6 permselectivities above the Knud-
sen factor (up to 30). Finally, Tiscareño et al. [22] used a
centrifugal system for the synthesis of zeolite A membranes
with the double objective of achieving solution renewal and
at the same time driving the crystal nuclei formed in the ho-
mogeneous phase towards the support. In this way, crystal
nuclei were deposited before they reached a size that would
be difficult to accommodate into the growing membrane, thus
promoting the formation of a higher quality zeolite layer.
In this work, we propose a new semi-continuous procedure
to prepare NaA zeolite membranes over tubular supports in
a single step, in a reaction vessel where the synthesis solu-
tion is rapidly removed from the membrane environment at
regular intervals, and simultaneously replaced by the same
volume of fresh gel. This represents a compromise between
a batch process, in which there is a significant depletion of
reactants over time, and a process with a continuous feed of
low flow rate, where a certain variation of concentration along
the support is inevitable, likely leading to inhomogeneous
growth of the membrane. The aim of this work is to improve
the synthesis concerning the above-mentioned problems of
unwanted synthesis in the bulk of the liquid phase and poor
crystal intergrowth due to local exhaustion of reactants in the
autoclave. At the same time, this procedure allows a better
control of the composition of the reacting mixture and avoids
heating and cooling steps between synthesis, thus improving
the feasibility of the scale up.
2. Experimental
2.1. Membrane preparation
Zeolite NaA membranes were hydrothermally synthe-
sized on the external surface of ␣-alumina symmetric tubes
of 7 mm ID and 10 mm OD, with a nominal pore size of
∼1900 nm. These supports were first enamelled at both ends
 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150
defining a permeation length of approximately 5 cm. A seed-
ing step was ensured, by rubbing the outer support surface
with zeolite A crystals with a mean size of 1 ␮m. Sec-
ondary growth of the seed layer deposited on the support
tubes was carried out for 5 h at approximately 90 ◦ C us-
ing a synthesis gel with the following molar composition:
1.8SiO2 :1.0Al2 O3 :3.9Na2 O:273H2 O.
SiO2 was supplied as SiO2 ·NaOH (27 wt.% SiO2 , 14 wt.%
NaOH and 59 wt.% H2 O; from Aldrich) and Al2 O3 as
Al2 O3 ·3H2 O (from I.Q.E). Once the Al precursor was com-
pletely dissolved in NaOH solution (50 wt.%, prepared from
NaOH pellets 99% pure supplied from Merck) under vig-
orous stirring at 60 ◦ C, the Si precursor was slowly added,
keeping constant the temperature to avoid the formation of
aggregates. The synthesis gel was then poured onto a ther-
mally insulated stainless steel vessel.
The experimental set-up employed for the semi-
continuous synthesis of NaA zeolite membranes, is shown
in Fig. 1A. Fresh gel was supplied from a vessel pressur-
ized with dry nitrogen (around 10 bar), by removing a known
Fig. 1. (A) Experimental set-up for the semi-continuous synthesis of NaA zeolite membranes; (B) scheme of the Teflon-lined autoclave used.
143
gel volume from the autoclave (10 cm3 ) corresponding to the
length of pipe between electro-pneumatic valves E1 and E2.
The length and diameter of this piece of pipe could be changed
in order to adjust the renewal volume to a desired value. Af-
ter each renewal step, compressed air was admitted through
valve E3 for the complete removal of the discharged fluid.
To avoid corrosion in case the electrovalves were reached by
the highly alkaline synthesis solution, an intermediate vessel
filled with cold paraffin was used as a buffer. The renovation
rate was set at the desired value by the electrovalves control
unit.
A first series of synthesis revealed the presence of sig-
nificant temperature variations in the synthesis vessel due
to the low temperature of the feed. This was corrected by
the use of a heating tape wrapped around the gel container
and pipelines connected to the autoclave inlet, which pre-
heated the feed to a constant temperature of around 60–65 ◦ C.
This temperature was high enough to reduce thermal upset
upon feed introduction, and low enough to avoid synthesis in
the inlet pipe. A more detailed scheme of the Teflon-lined
144 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150

Fig. 2. Experimental set-up for the pervaporation and vapor permeation system.

autoclave immersed in the thermostatic bath is shown in

Fig. 1B. The reaction temperature was monitored by means
of two thermocouples positioned in the upper (top) and lower
sections (bottom) of the autoclave in order to register temper-
ature fluctuations with gel introduction. The membrane was
fixed in vertical position by means of a Teflon plug in such a
way that the points for temperature measurement were close
to the zeolitic layer growing on the external seeded surface
of the alumina support.

2.2. Membrane characterization and testing

The experimental set-up for the PV and VP of wa-

ter/ethanol mixtures is shown in Fig. 2. In both cases, the
membrane module was immersed in a temperature-controlled
bath (SELECTA, PRECISTERM) of silicone oil (Rhodosil).
The temperature was measured with a thermocouple located
in the membrane tube side (permeate). An HPLC pump
(SHIMADZU, LC-10AT VP) was used to feed 0.083 ml/s
(5 ml/min) of a water/ethanol (10/90 wt.%) liquid mixture to
the outer side of the membrane, through a heating coil im-
mersed in the thermostatic bath. For PV measurements, the
pressure at the retentate side was adjusted to values higher
than the mixture vapor pressure (around 6 bar at 125 ◦ C),
whereas for VP measurements a pressure of 1.1 bar at 140 ◦ C
was used. In either case, the vacuum (around 0.5 mbar) at the
permeate side achieved by a rotary pump (TELSTAR, G6)
provided the driving force for diffusion and pervaporation.
Both the feed and the liquid collected in the liquid-N2 traps
were analysed in a gas chromatograph (VARIAN, 3400) with
TCD and FID detectors. The H2 O/ethanol separation factor Fig. 3. Temperature profiles vs. synthesis time at 1 renewal every 16 min for
was calculated as the quotient between the ratios of the weight feed gel introduced at: (A) room temperature; (B) 60 ◦ C.
fractions of water and alcohol in the permeate and feed sides,
respectively.
The phases present in the NaA membranes were charac- autoclave after synthesis and of the membrane top lay-
terized by X-Ray diffraction (XRD) analysis (Rigaku/Max ers. The membranes were also examined by scanning
diffractometer Cu K␣ radiation and graphite monochro- electron microscopy, SEM (JEOL JSM-6400 operating at
mator) of the powders collected at the bottom of the 20 kV).
 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150 145

Table 1
Autoclave temperatures measured during hydrothermal synthesis of NaA zeolite membranes using the semi-continuous system
Preheating Renewal rate (min−1 ) Top temperatures (◦ C) Bottom temperatures (◦ C)
Minimum Maximum Average Minimum Maximum Average
NO 1/16 61 94 89 37 99 75
YES 1/16 61 96 93 72 100 92
NO 1/20 61 98 90 41 103 82
YES 1/20 59 96 93 67 99 90
NO 1/25 61 94 89 43 101 92
YES 1/25 61 97 90 76 105 96

3. Results and discussion
3.1. Semi-continuous synthesis of NaA zeolite
membranes
All the membranes prepared in this work have been syn-
thesized at a temperature of approximately 90 ◦ C, measured
at the top of the autoclave. After initial batch synthesis ex-
periments with the above-described gel composition, XRD
analysis (not shown here) of the powders collected at the
bottom of the autoclave after synthesis, revealed that an in-
duction period of 3 h was necessary for the development of
LTA structure. Therefore, a synthesis period of 5 h was se-
lected as the duration of the synthesis in this work.
Fig. 3A shows the evolution of the top and bottom temper-
atures in the autoclave for a given renewal rate (1/16 min−1 )
when the feed was not preheated. A sharp temperature de-
crease is observed at the bottom of the autoclave after every
fresh gel addition, reaching values as low as 37 ◦ C. A period
close to 15 min is needed for the temperature to recover its
original value at this location, and almost immediately a new
addition of fresh gel takes place, meaning that a stable temper-
ature is never reached at the bottom of the autoclave. Fig. 3B
shows the results of an analogous experiment with preheat-
ing of the gel (to approximately 65 ◦ C) before entering the
autoclave. With this modification it can be seen that, while a
drop of temperature at the bottom of the autoclave still occurs
upon gel renewal, the range of temperature variation within
the autoclave has been notably narrowed. Interestingly, the
effect of gel renewal upon the temperature at the top of the
autoclave is now more marked, and a clear coupling between
the temperature oscillations of both thermocouples can be
observed. This is probably due to the fact that in the first case
(cold gel supply) mixing in the vessel is more limited due to
the higher density of the cold feed, which produces a layer
of denser solution that tends to stay near the bottom of the
autoclave.
Table 1 summarizes the average autoclave temperatures
as well as the minimum and maximum temperature values at
the top and bottom of the autoclave for different experimen-
tal conditions (renewal rate, gel preheating). Again, a clear
improvement of temperature control, especially at high re-
newal rates, is obtained with a preheated feed. Moreover, gel
preheating gives rise to membranes of a significantly higher
quality, as will be shown below by the results of pervapo-
ration experiments with water–ethanol mixtures. In spite of
this, inlet temperatures higher than 65 ◦ C were not used, to
avoid synthesis occurring before the gel enters the autoclave,
with the associated problems of reagent exhausting, and crys-
tallization and possibly plugging in the inlet duct.

Table 2
Some details of the synthesis procedure and characteristics of the NaA zeolite membranes prepared in this work
Sample Gel preheated Renewal rate (min−1 ) Zeolite loading (mg/g) N2 permeance (mol/m2 s Pa)
MC13 NO 1/13 5.2 6.8 × 10−8
MC16 NO 1/16 6.8 5.9 × 10−8
MC20 NO 1/20 6.6 6.6 × 10−8
MC25 NO 1/25 6.3 5.0 × 10−8
MC38 NO 1/38 5.6 1.4 × 10−8
MC75 NO 1/75 5.5 2.0 × 10−8
MH13 YES 1/13 8.1 1.2 × 10−8
MH16A YES 1/16 7.6 6.7 × 10−10
MH16B YES 1/16 9.0 1.5 × 10−9
MH20A YES 1/20 8.1 1.4 × 10−9
MH20B YES 1/20 6.9 3.8 × 10−10
MH20C YES 1/20 8.1 7.8 × 10−10
MH25 YES 1/25 8.0 1.3 × 10−9
MH38 YES 1/38 6.4 2.0 × 10−9
MH300a YES – 4.8 4.0 × 10−8
a Sample synthesized using the discontinuous approach, i.e., no renewals during the 5 h synthesis.
146 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150

Fig. 4. SEM micrographs of sample: (A) MC20 top view and cross-section; (B) MH20 top view and cross-section; (C) MH13 top view and cross-section.

3.2. NaA zeolite membrane characterization
Table 2 summarizes some of the main characteristics
(gel preheating, renewal rate, zeolite loadings and nitrogen
permeance) for the membranes used in this work. For iden-
tification purposes, the samples synthesized without gel pre-
heating were denoted using “MC”, whereas “MH” was used
when the gel was preheated. Both, weight gain and nitro-
gen permeance, were measured after drying the membrane
at 100 ◦ C overnight. This is only a mild drying treatment
and therefore it is likely that, due to the hydrophilic charac-
ter of the NaA zeolite membrane, variable amounts of water
could remain adsorbed in the micropores when the perme-
ance measurements were carried out, affecting the values
given. Therefore, the permeances given in Table 2 have to
be taken as lower limits (i.e., the nitrogen permeance with a
completely water-free membrane could be higher), but they
can still be used as a first indication of membrane quality
since a significant concentration of defects would translate
into larger permeation fluxes. In general terms, higher zeo-
lite weight gains (6.0 mg/g versus 7.4 mg/g on average) and
lower values of nitrogen permeance (4.6 × 10−8 mol/Pa s m2
 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150 147

versus 7.4 × 10−9 mol/Pa s m2 on average) were detected Table 3

Water/ethanol separation performance in VP and PV of some of the NaA
when the gel was preheated. Additionally, sample MH300, zeolite membranes prepared in this work
which corresponds to a synthesis carried out batchwise (i.e.,
Sample Vapor permeation Pervaporation
with the same gel composition but without gel renewal), ex-
hibits permeance and weight gain values similar to those of Water flux Separation Water flux Separation
the “MC” series. The zeolite weight gains for the MH mem- (kg/h m2 ) factor (kg/h m2 ) factor
branes in Table 2 were on average 30% higher than those for MC38 0.89 362 2.9 371
the MC series, a result expected in view of the higher average MC20 0.81 1052 2.2 94
MH38 0.80 2863 3.8 163
temperatures in the autoclave. On the other hand, the nitro- MH25 0.80 839 3.1 1307
gen permeances measured for the MH membranes were one MH20B N/A N/A 3.8 3603
order of magnitude lower, indicating a lower concentration MH20C 1.0 3162 N/A N/A
of defects (a higher membrane quality) for the membranes MH16A 0.65 2736 2.5 1046
prepared with a preheated gel.
These observations are in good agreement with SEM anal-
ysis as can be seen in Fig. 4A and B, where MC20 and seeded surface seems to be less ordered, and the membrane
MH20B, both prepared with one gel renewal every 20 min, thickness achieved is only around 8 ␮m (8 microns), giving
are compared. The MC20 micrographs reveal the presence a higher permeation flux with respect to MH20B.
of amorphous material among cubic crystals of NaA (with Fig. 5 shows XRD patterns obtained from the analy-
a size around 5 ␮m (5 microns)) forming an irregular layer sis of the external surface of MH13, MH20B and MC20
with a thickness of ca. 15 ␮m (15 microns) on the external
surface of the alumina support. On the contrary, amorphous
material seems to be absent from the membrane MH20B top
layer, where two types of crystals can be distinguished: larger
cubic crystals 5–10 ␮m (5–10 microns) in size, and smaller
units (3 ␮m (3 microns) edge) covering the inter-boundary
gaps. These crystals form a homogeneous, well-intergrown
layer with a thickness around 10 ␮m (10 microns). Increas-
ing the renewal rate to 1/13 min−1 , i.e., MH13, renders a
base layer of cubic crystals around 2 ␮m (2 microns) in size
(see left part of Fig. 4C) coexisting with larger units (around
5 ␮m (5 microns) edge). Some of these larger crystals seem
almost detached from the continuous zeolite layer, suggesting
that they may have nucleated in the bulk of the liquid phase
(aided by the higher average concentration of reactants that
is obtained with a higher renewal rate) and then precipitated
onto the zeolite film. The growth of zeolite crystals over the

Fig. 6. (A) Water permeation fluxes and (B) water/ethanol separation factors
Fig. 5. XRD patterns of zeolite NaA membranes synthesized with the semi- as a function of gel renewal rate for NaA zeolite membranes synthesized by
continuous method under different conditions. The stars denote the reflec- the semi-continuous method, using preheated gel. PV conditions: 6 bar and
tions corresponding to the ␣-Al2 O3 commercial support. 125 ◦ C on the retentate side.
148 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150

Table 4
Some examples extracted from the literature of pervaporation performance for different zeolite membranes
Zeolite Mixture (A/B) T (◦ C) Concentration of A (wt.%) Separation factor ␣(A/B) Flux (kg H2 O/m2 h) Support Reference
NaA H2 O/i-propanol 70 10 8500 0.82 Zirconia sheets [6]
NaA H2 O/ethanol 50 10 46 000 0.77 Mullite tubesa [7]
NaA H2 O/ethanol 75 10 42 000 2.08 Mullite tubesa [7]
NaA H2 O/ethanol 120 10 47 000 8.37 Mullite tubesa [7]
NaA H2 O/ethanol 105 10 30 000 4.53 Mullite tubesa [9]
NaA H2 O/ethanol 75 10 10 000 2.15 ␣-Al2 O3 tubes [10]
NaX H2 O/ethanol 75 10 410 0.98 Mullite tubes [11]
NaY H2 O/ethanol 75 10 130 1.59 Mullite tubes [11]
Silicalite Ethanol/H2 O 60 5 58 0.760 S.S. disks [12]
NaX H2 O/ethanol 75 10 400 0.5 ␣-Al2 O3 disks [21]
NaA H2 O/ethanol 75 10 23 000 2.5 ␣-Al2 O3 disks [21]
Mordenite H2 O/i-propanol 75 10 3360 0.1 ␣-Al2 O3 tubes [25]
Silicalite i-Propanol/H2 O 80 5 25 0.11 ␣-Al2 O3 disks [26]
ZSM-5 H2 O/I-propanol 80 5 501 0.14 ␣-Al2 O3 disks [26]
Mordenite H2 O/ethanol 150 10 210 1.1 ␣-Al2 O3 tubes [27]
NaA H2 O/ethanol 125 10 3603 3.80 ␣-Al2 O3 tubes This work
a Al2 O3 :SiO2 ratio equal to 65:35.

membranes. The comparison with the NaA zeolite pattern
[23] shows that pure zeolite with the LTA-type structure is
the only crystalline phase present in all the samples analyzed.
When the crystals collected at the bottom of the autoclave af-
ter synthesis were examined by XRD, NaA zeolite was again
the only phase found, independent of the renewal rate em-
ployed. Finally, when the peak intensities of characteristic
diffractions of ␣-alumina and NaA (at 35.3◦ and 24.2◦ , re-
spectively) were compared, the ratio was around three times
higher for samples MH13 and MH20B than for MC20 (with-
out preheating). This is in agreement with the higher amount
of crystalline material evidenced by the SEM micrographs
for the membranes prepared with preheated gel.
3.3. Water-ethanol separation performance
Table 3 shows the water/ethanol separation performance
in VP and PV experiments of some of the membranes pre-
pared in this work. After an initial stabilization period of
approximately 2 h, the membranes showed a stable perfor-
mance for the duration of the experiments (up to 10 h). In VP
tests, H2 O/ethanol separation factors ranged between 362 and
3162, and water fluxes between 0.65 and 1 kg/h m2 , depend-
ing on the gel preheating and the renewal rate employed. On
the other hand, in PV experiments water fluxes at least double
than those in VP tests were measured, as could be expected,
given the higher driving force in pervaporation. Despite the
differences in nitrogen permeance shown in Table 2, the PV
and VP fluxes are in a relatively narrow range (similar results
were observed by Okamoto et al. [10]).
Table 3 also shows that samples prepared with a preheated
gel usually give considerably higher separation factors, com-
pared to their cold-gel counterparts. This effect is clearer with
VP measurements (3162 versus 1052 for M20 membranes,
and 2863 versus 362 for M38 membranes, respectively). The
separation properties of hydrophilic zeolite membranes for
dehydration of solvents by PV can be explained by the so-
called adsorption-diffusion model [3,8,24]. This process in-
volves three-steps: (i) adsorption of the components onto the
membrane, (ii) diffusion of the components across the mem-
brane, and (iii), finally, desorption of the components into the
vapor phase at the permeate side. Separation takes place be-
cause selective adsorption of water, both on the zeolite pores
and also on small defects between neighboring crystals, hin-
ders the permeation of the alcohol. This mechanism is consis-
tent with the separation properties found for the membranes
prepared in this work.
Fig. 6A and B illustrate the influence of the renewal rate
on the pervaporation performance (water flux and separation
factor) of membranes prepared with the preheated gel. A con-
tinuous line was drawn across the average values obtained in
each case, while the dotted lines join the maximum and mini-
mum values registered for a given renewal rate. The beneficial
effect of gel renewal is clear from the results of Fig. 6B: under
otherwise identical conditions, an H2 O/ethanol separation
factor of only 54 was obtained in 5-hour batch syntheses with-
out gel renewal. Also, it can be seen that an optimum value
exists for the separation factor: at renewal rate of 1/20 min−1 ,
a clear maximum with a value of 3600 was obtained in the
H2 O/ethanol separation factor. The trend regarding the per-
meation flux is less clear, but nevertheless the maximum av-
erage value for the permeation flux (3.8 kg H2 O/h m2 ) was
also obtained at this renewal rate. SEM observations also in-
dicate that the best intergrowth and crystallinity correspond
to the membranes prepared at 1/20 min−1 renewal rate.
The nucleation and growth of crystals in solution is of-
ten put forward as an example of a complex phenomenon
under the influence of many factors, such as variations of
reactant concentration in the solution around the crystals, lo-
cal variations of temperature, degree of mixing, presence of
impurities and existence of other surfaces capable of provid-
ing additional nucleation sites. Growing zeolite crystals on a
 M.P. Pina et al. / Journal of Membrane Science 244 (2004) 141–150
porous support under conditions that favour their intergrowth
into a membrane adds an extra degree of complexity to the
process. The procedure used in this work attempts to facili-
tate synthesis by minimizing the variations of concentration
in the bulk synthesis solution with time with respect to batch
processing. Periodic gel renewal is also useful to improve
mixing in the synthesis vessel, reducing the concentration
gradients that always develop in the vicinity of growing crys-
tals. However, the results obtained seem to indicate that there
is an optimum renewal rate, and increasing the renovation
rate beyond that value leads to a decrease in the quality of the
membranes obtained. A major factor in this decrease may be
the nucleation and growth of crystals in the bulk of the syn-
thesis solution, aided by the increased gel concentration that
results from more frequent gel renewal. The crystals formed
in the bulk grow to a certain size and eventually precipitate
onto the developing membrane, where they cannot be easily
integrated, giving rise to the formation of defects.
Finally, Table 4 compares the PV separation properties
obtained for the membranes synthesized in this work (at
1/20 min−1 renewal rate) with some of the best PV results
reported for zeolite membranes, extracted from a literature
survey. While pervaporation results from different labora-
tories are often difficult to compare because of the differ-
ent experimental conditions used, it can be said that the
membranes obtained with the semi-continuous system used
in this work are among those with the best pervaporation
performance.
4. Conclusions
A novel semi-continuous system for the preparation of
good-quality zeolite-A membranes has been developed, in
which the synthesis gel is removed from the membrane en-
vironment at periodical intervals while at the same time an
equivalent amount of fresh gel is added to the synthesis ves-
sel. This provides a rational way to control the preparation
conditions by better approaching a constant concentration
during the synthesis process. The problem of temperature
upset related to the introduction of a colder fluid in the syn-
thesis vessel has been minimized by choosing a sufficiently
high feed temperature that is nevertheless compatible with
avoiding synthesis taking place outside the autoclave.
There is still considerable room for optimization of the
synthesis conditions. Thus, the feed concentration used has
been chosen within the interval of initial concentrations typi-
cally employed in successful batch syntheses of zeolite mem-
branes, but it must be taken into account that in these experi-
ments a considerable depletion of reactants takes place. Keep-
ing a nearly constant concentration in the vessel probably al-
lows the use of different (lower) feed concentrations and/or
temperatures, leading to improved membranes. In spite of
this, excellent results have been obtained in pervaporation ex-
periments (3.8 kg H2 O/h m2 with a H2 O/ethanol separation
factor of 3603), indicating that the semi-continuous synthesis
149
is suitable for the scale up of zeolite membrane preparation
processes.
Acknowledgements
Financial support from MCYT, Spain, is gratefully ac-
knowledged.
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