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Microporous and Mesoporous Materials 115 (2008) 215–233

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Microporous and Mesoporous Materials
journal homepage: www.elsevier.com/locate/micromeso

Review

Zeolite membranes – Recent developments and progress
Juergen Caro a,*, Manfred Noack b
a
b

Leibniz University of Hannover, Institute of Physical Chemistry and Electrochemistry, Callinstr. 3-3A, D-30167 Hannover, Germany
Leibniz Institute for Catalysis at the University Rostock, Branch Berlin (former ACA), Richard-Willstätter-Str. 12, D-12489 Berlin, Germany

a r t i c l e

i n f o

Article history:
Received 31 January 2008
Received in revised form 4 March 2008
Accepted 6 March 2008
Available online 18 March 2008
Keywords:
Zeolite membrane
Oriented zeolite layers
Micro reactors
Membrane reactor
Process intensification
Gas separation
Mixed matrix membrane

a b s t r a c t
There is a continuous worldwide interest in zeolite membranes. On the one hand side, we can observe
increasing numbers of scientific publications. On the other hand, there are first industrial applications
of zeolite membranes in the de-watering of ethanol and i-propanol by LTA membranes. The remarkable
progress made in the preparation and characterization of zeolite membranes during the last few years
has stimulated several industrial R&D projects exploiting the shape-selectivity of zeolite membranes in
mass separation. Above the horizon of separation, several concepts like zeolite (micro) reactors look
promising for process intensification. Furthermore, functional zeolite layers can play an important role
in the nanotechnology era.
Ó 2008 Elsevier Inc. All rights reserved.

Contents
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2.

3.

4.

5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Novel synthesis concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Secondary growth on seeded supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Intergrowth supporting substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Crystallization by microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Stacking of silica nanoblocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Oriented zeolite membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.
Bi-layered zeolite membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Case studies of mixture separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Water separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Hydrogen separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Carbon dioxide separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
p-Xylene separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.
Alcohol separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Innovative applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Membrane reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Micro membrane reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Functional films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.
Mixed matrix membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

* Corresponding author. Tel.: +49 (511) 762 3175; fax: +49 (511) 762 1912.
E-mail addresses: caro@pci.uni-hannover.de (J. Caro), manfred.noack@catalysis.de (M. Noack).
1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.03.008

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To the authors knowledge. the seeds can grow in low concentrated solutions under suppression of secondary nucleation. DDR [32]. Caro. mechanically stable dielectrics. Ordered porous molecular sieve layers are believed to be important materials in the nanotechnology era with novel emerging applications [9.10]. MOR [23. FER [25]. AFI [33] and mixed tetrahedral–octahedral oxides [34–37]. supported zeolite layers have attracted intensive research efforts due to their potential applications as separation membrane. The power of the seeding technique was demonstrated by Matsukata et al. mixture separation and application. The use of seeded supports usually results in a c-orientation of the MFI layer but under certain conditions also for secondary growth the desired b-orientation can be obtained [43]. 2b) [52–55].1. Fig. Two principal methods are used to suppress homogeneous nucleation: (i) ‘‘Dry gel conversion” [39. and  Immersion of the dried support into a seed solution with a following thermal treatment of the seeded support to burn helping organic additives and to fix the seeds via de-hydroxylation to the support. There are four main ways to attach the seeds to the support:  Charging the support surface by pH control to achieve that seeds and support have opposite surface charges for an electrostatic attachment (see Fig. CHA [27]. M. traditional thermal separations [1].1 In between numerous zeolite membrane preparations are reported and substantial progress can be stated. MEL [26]. 1. solar cells and advanced batteries can be observed. worldwide activities on fuel cells. electrode. much less revolutionary actions are necessary when energy-intensive thermally driven separation processes are substituted by membrane–based ones. Trade name of EKA Chemicals. catalytic membrane reactor. Recently several pioneering papers on the prospects of zeolite films beyond the realm of separation for assembly of novel and complex functional materials including molecular sensors. The counter ions of the ammonium polymer are usually chlorides which go in the solution and negatively charged silica nano-particles are attracted. By decoupling the nucleation step (at high supersaturation) from crystal growth (at low supersaturation). masking techniques can be used to avoid the penetration of seeds and synthesis gel into the support pores. high-flux membranes with a thickness of about 0. here we focus on latest developments after 2000 in synthesis. Introduction Increasingly energy issues become important and as an answer. Novel synthesis concepts clear solution or an aqueous gel contained in an autoclave for crystallization temperatures of 180 °C for MFI type membranes or of 90–100 °C for FAU or LTA membrane preparations. However. chemical sensor.5 lm could be prepared [45]. The cross-section of the simply 2. FAU [19–22]. 3 shows the cross-section of a typical supported silicalite-1 membrane synthesized by a two-step seeded crystallization on the surface of a 1 cm tubular titania support with asymmetric structure. high-resolution scanning electron microscopy (HR-SEM) can reveal different features of a zeolite membrane. the use of seeds offers a way to control the growth of a zeolite layer on a surface. opto-electronic device. examples are the preparations of zeolite membranes of types LTA [12–18]. 2 Diallyl dimethyl ammonium chloride. a polyamine.24]. In the last decade. 2a) [49–51]. Since a comprehensive ab initio picture of the field of zeolite membranes would be too volumous. The energy required to achieve some large-scale separation tasks can be an order of magnitude lower using membranes vs. Secondary growth on seeded supports In the direct hydrothermal in situ-crystallization [38] the support is immersed in the zeolite synthesis solution which can be a 1 Remark of the editor: this article has been cited 231 times till November 2007 and that it ranks as the third most cited article in Microporous and Mesoporous Materials. Development of articles in open literature with (zeolit* OR molecular sieve) AND (membrane* OR coating OR film). Our previous review entitled ‘‘Zeolite membranes – state of their development and perspective” [11] has been widely read and cited. 1). [46] showing that mordenite or ZSM5 type membranes could be prepared from identical organic-free aluminosilicate solutions under the same hydrothermal conditions by using either mordenite or MFI seeds. Like in the direct in situ-crystallization of zeolite membrane. the first paper on seeding appeared in 1993 [48]. Depending on the sample preparation. 2. 4 To avoid any acidity. We hope that this updated review will be beneficial to researchers in the field. the first patent to seed a support surface was submitted in 1994 [47]. and novel reaction–diffusion devices appeared [2–8]. SAPO-34 [28–31]. low dielectric constant material for use as electrical insulator. protection or insulation layer or as host for the organization of functional guest molecules (see Fig. the support was protected from the synthesis solution and using colloidal nucleation seeds followed by hydrothermal growth.216 J. either as vapour-phase transport method when structure-directing agent (SDA) is in the vapour but not in the dry supported parent gel [41] or a steam-assisted crystallization with a dry gel containing the SDA [42]. 3 .  Electrophoretic deposition of nanosized seeds on solid supports [56–60]. 1. By a sophisticated PMMA – wax treatment in a laminar flow bench.40].44]. The use of seed crystals facilitates the formation of zeolite membranes since a seeded support grows to a pure-phase zeolite membrane more easily even when the crystallization conditions and the chemical batch composition are not optimum. in special cases porous titania and zirconia supports can be used. However.  Charging the support surface by adsorption of positively charged cationic polymers like Poly-DADMAC2 or Redifloc3 to adjust different zeta potentials between the ceramic support4 and the zeolite nano-crystals to be attached as seeds (see Fig. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 Fig. In this case no opposite surface charges can be generated by pH control and a positive surface charge can be generated by adsorption of positively charged macromolecules. and (ii) Seeding (secondary growth) using externally prepared seeds [43.

In the marked area in (a). 3. the membrane with the highest Al-content shows the highest residual nitrogen flux and has the lowest separation factor. Fig. mechanically broken membrane shows clearly the columnar structure and indicates that the silicalite-1 crystals forming the membrane layer start to grow from the top of the seed layer (Fig. 2. 3b). It is found by permporometry that an increasing Al-incorporation into the MFI structure gives membranes with high concentrations of defects. This mechanism seems to cause the poor intergrowth of Al-containing ZSM-5 crystals to a continuous gas-tight membrane layer in comparison with the successful preparation of the Al-free silicalite-1 membranes. M. On the other hand. at a certain p/ps ratio the zeolite pores are filled and the remaining flux of the inert gas can be contributed exclusively to non-regular zeolite defect pores. the silicalite-1 membrane (Si/Al  1) has no measurable residual nitrogen flux at p/ps > 0.2. If the cross-section of the same membrane is carefully prepared by using a Cross-Section Polisher operating with Ar ions. there is good electrostatic attachment between pH 3–7. to crystallize thin defect-free Al-containing MFI layers as postulated in recent papers [67. Searching for the reasons for this experimental finding. A remaining He or N2 flux indicates the presence of defect pores in the meso or macropore range.05 and shows the highest separation factor. according to the Kelvin equation. The basic concept of permporometry is that a binary feed of an inert non-condensable and less adsorbing gas (He.J. Zeta potential of alumina and silica (a) and titania and silica (b) nanoparticles suspended in 0.01 m KCl as electrolyte as a function of the pH at 25 °C (the alumina and titania particles simulate the Al2O3 and TiO2 supports and the silica nano particles the silicalite-1 seeds). That is to say. an increase of the negative surface charge (zeta potential) of ZSM-5 crystals with enhanced Al-content was found.5. it is assumed that the transport and the attachment of the precursors into narrow slits is hindered. The highly adsorbing vapour such as n-hexane for hydrophobic membranes like silicalite-1 or water for hydrophilic membranes like FAU or LTA is mixed to the inert gas with increasing p/ps ratios. Consequently. The vapour fills the regular micropore system of the membrane and blocks them for the passage of the less adsorbing inert gas. This picture corresponds with the evolutionary growth selection model [61–66] which usually provides a c-orientation of the MFI membrane. By . It seems to be a general problem. 4). Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 a 217 b Fig.68]. Caro. SEM of the cross-section of a silicalite-1 membrane on the surface of a tubular titania support prepared by seeded crystallization: simply mechanically broken (a) and prepared by using a Cross-Section Polisher operating with Ar ions (b). Since the silica precursors in the synthesis solution are negatively charged like the growing ZSM-5 layer. it can be seen that the c-oriented columnar structure is also well intergrown and there are no observable major voids or cracks (Fig. 5). Intergrowth supporting substances From permporometry and mixture permeation studies on a ZSM-5 membrane series of different Al-content it was found that the intercrystalline defect transport is linked to the Al-content (Fig. 3a). 2. Because of the instability of the silicalite-1 nanoparticles one has to operate at pH 7–8. therefore. N2) and a vapour which prefers to fill the regular micropores is sent as a cofeed through the membrane (Fig.

Furthermore. adsorption of intergrowth supporting substances (ISS) the strong negative surface charge can be compensated to the isoelectric point (Fig. large single crystals were obtained in relative short times. Crystallization by microwave heating Microwave-assisted crystallization provides a very efficient tool for preparing a variety of zeolite materials within short times [72]. microwave heating is understood and can be applied in zeolite membrane synthesis [79]. mix this gas stream with the pure non-adsorbing gas thus finetuning the p/ps and send the blended gas through the membrane. 5. Si/Al = 270 ? a = 15. for gases. 2. Suitable ISS are small positively charged molecules. The permporometry measurements correlate very well with the mixture separation factor a(n/i-pentane) on these ZSM-5 membranes (50/50% mixture. 6). This ISS concept was first developed for Al-containing MFI membranes (ZSM-5) and later successfully transformed to the synthesis of LTA and FAU membranes. There was some mystery about the molecular understanding of microwave heating. e. an improvement of the permeation selectivity of LTA and FAU membranes was found (Table 2). In the beginning of the 1990s good experience in zeolite crystallization was made by using microwaves for heating the autoclaves. The mixture separation factor is defined as a (i. calculate the relative decrease of the inert gas flux as shown in Fig. The improvement of the LTA and FAU membrane quality can be concluded from permporometry measurements (Fig. respectively. Therefore. By variation of the temperature and the duration of the microwave treatment a maximum in the n-/i-butane ideal permselectivity for a microwave treatment for 2 h at 160 °C was found experimentally. Pioneering papers reported the successful synthesis of MFI (ZSM-5) and FAU(Y) [73. Increasingly. M. n-hexane for the hydrophobic silicalite-1 membrane and water for the hydrophilic LTA membrane. Evaluating different ISS.1. Nevertheless.01 m was found out to be optimum [69]. Permporometry characterization of MFI membranes of different Si/Al-ratio [69] showing that the residual nitrogen permeance as a measure of the defect concentration increases with the Al-content. It seems that there is no intrinsic microwave effect which leads to a reduction of the crystallization time compared to conventional heating if the latter can be done quick enough. there are other microwave effects which originate from the fast energy input which brings the system quickly to the crystallization temperature and suppresses kinetically the formation of nuclei. Recent progress was achieved in the microwave assisted hydrothermal synthesis of the silicalite-1 seeds for the membrane preparation [80] (Fig. Fig. Surprisingly. the silicate species are kinetically not in the thermal equilibrium. After addition of hexamethyl ethylene diammonium di-jodide (HMEDA-J2) (0. 4. LTA and FAU membranes can separate water/organic mixtures in an excellent way but they fail in shape-selective gas separations. stable in the alkaline region during the membrane synthesis and which can be decomposed by calcinations [69]. 110 °C): Si/Al = 119 ? a = 1. 6.g. Measure the relative decrease of the flux of the inert gas for increasing p/ps of the well adsorbing species.3. AFI (CoAPO-5 [76]) and (AlPO4-5 [77. Caro. send a part of the non-condensable gas through a saturator filled with the well adsorbing liquid. Therefore. Zeta potential measurements on the Al-rich zeolite crystals LTA and FAU also show a strong nega- tive surface charge like it was found for Al-rich MFI crystals (ZSM-5). By using an ISS. many attempts were made to improve the separation properties of LTA and FAU membranes. LTA and FAU(X) [75].74]. a b saturator N2 N2 N2 flux = 100% Fig. 7). However. Silicalite-1 membranes with a controllable thickness and high crystallinity can be derived within a few hours when seeded supports are microwave heated. HMEDA-J2 in a concentration of 0. Zeta potentials of suspended MFI crystals of different Si/Al-ratios at room temperatrure.g. the LTA and FAU membranes prepared with ISS are still far from being defect-free and their permselectivities are found in the range of the Knudsen factor. 8) and the silicalite-1 membrane crystallization itself [81] (Table 3). Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 Fig.01 m in the electrolyte) as an ISS. because of the accelerated heating of the synthesis mixture.78]). However. by using induction heating. Si/Al = 1: ?a = 120 [67]. the zeta potentials become less negative and are near to the isoelectric point [69]. e.j) = (yi: yj)/(xi: xj) with y and x as mole fractions i and j in the permeate (y) and feed (x) [70]. Scheme of a permporometry experiment: (a) Measure the flux of an inert non-condensable gas like He or N2 through a porous membrane and set this 100%. elongated heating at high temperatures results in a dissolution of . (b) Select a suitable vapour that is well adsorbed by the zeolite. By adsorption of an ISS this negative zeta potential can be shifted near to the isoelectric point which improves the intergrowth of the seed crystals on the support to a continuous membrane layer.218 J. 4. the effect of using ISS on the membrane quality was studied for the ISS HMEDA-J2 in the preparation of MFI membranes of different Si/Al (Table 1).

and then crystal growth by propagation through the amorphous primary particles (size of about 50 nm) goes on and.025 [84].4  108 2. Caro. Specifically. [85–87] who developed the ‘‘in situ aging – microwave synthesis” method [88. The clear solution synthesis of silicalite-1 proved to be a particularly interesting system to clarify the zeolite formation [90] and TEM has shown to be a particularly powerful technique for this investigation.7 3. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 190 Si/ Al 170 180 57 96 H2/i-butane H2/SF6 Without ISS With ISS Without ISS With ISS Without ISS With ISS 2.7  107 3. finally these particles transform into LTA crystals of about the same size. M. However.7 5.4 5.1 2.5 4. Stacking of silica nanoblocks The crystallization mechanism of zeolites has been a research topic since the first successful zeolite synthesis. synthesis” (Fig.3 2. j) is calculated as the ratio of the single component fluxes PS (i. the permselectivities of the LTA membranes are only slightly superior than the Knudsen separation factor. differential microwave absorption and non-equilibrium contributions to reactions may limit the formation of undesired phases in comparison with conventional heating. This procedure takes into account that the support does not absorb microwaves and remains unheated but the microwaves selectively couple with the gel layer because of its higher dielectric loss factor. In this way.5  108 14 15 42 3 The permeance P is given in mol m2 s1 Pa1.3  108 5.2 2.0 1.1  106 6.1  107 2.5 68.3 4. 2. By different synthesis temperatures and different methods for seeding the support.4 TPAOH: 19.7 5. 8.4. the ideal or permselectivity PS is the ratio of the single gas permeances. The gel layer formed is in situ aged in an air conditioned oven. 7. j) = JiJ/Jj [70].7  108 7. Novel approaches are the attempts to prepare hydrophilic H-SOD5 membranes by microwave-assisted crystallization [83] and to insert additives such as titanium exclusively within the MFI membrane network.8 2.4  107 2.1  108 4. Preparation of silicalite-1 nano-crystals in a two-step-synthesis by microwave heating. min (at T2= 130 °C) Table 1 Increase of the permselectivities PS derived for different gas pairings from the corresponding single gas fluxes Ji at 105 °C for two MFI membranes when HMEDA-J2 is used as ISS [69] 120 10 110 100 25 75 125 Particle size. °C (at t2= 60 min) Permselectivity PS H2/n-butane 70 60 50 160 150 40 140 30 130 20 t2.7  109 9.0 12. the sol of the composition SiO2: 0. Rapid heating rate.9 2.5 the membrane formed. The ‘‘in situ aging” step was found to be necessary for a successful microwave synthesis.3 3.1 128. T2. High-quality LTA membranes could be synthesized with high reproducibility. Table 2 Comparison of the permselectivities PS derived from single gas permeances at 105 °C for FAU and LTA type membranes synthesized with and without HMEDA-J2 as ISS [71] Type H2/n-butane H2/i-butane H2/SF6 Without ISS With ISS Without ISS With ISS Without ISS With ISS Without ISS With ISS 2.3 2. up a molar ratio Ti/(Ti + Si) = 0.219 J. During the following microwave heating.6 3. oriented silicalite-1 layers with a (1 0 1) channel orientation are obtained [82].3 562 49 2. After maturation/nucleation at T1 = 80 °C for t1 = 90 min at a microwave performance of 250 W (not shown here). these pre-nuclei rapidly and simultaneously develop into crystal nuclei. Permselectivity PS H2/CH4 FAU LTA 130 °C/2 h 150 °C/2. despite this remarkable progress. 9).5 h 160 °C/2 h 180 °C/2 h Permeation temperature 21 °C H-SOD is hydroxy sodalite.4 2.5 H2O: 4 C2H5OH was crystallized in a second microwave heating step (shown here) varying at constant temperature T2 of 130 °C the duration t2 of microwave heating (right ordinate) and varying the temperature T2 for constant t2 = 60 min (left ordinate) (adapted from [80]).2 6.2  107 2.6 98.7  107 3. compact LTA zeolite membranes of spherical grains with undefined crystal facets are formed. Improvement of LTA and FAU membrane quality by using the ISS HMEDA-J2 demonstrated by permporometry [71]. nm 175 0 225 Fig. contains plenty of pre-nuclei. For the permeation data see Table 2.5  107 2.5 53 1. TEM has revealed the spontaneous formation of precursor . This process is repeated in a so called ‘‘second-stage 5 Permeation temperature 200 °C P n-butane P i-butane PS P n-butane P i-butane PS 1. A remarkable progress in the utilization of microwave heating was achieved by Yang et al.4  107 5.7 3.3 3.7  107 19 8.6 The permselectivity (ideal selectivity) PS(i.89].1  109 1. In a ‘‘first-stage synthesis”. Table 3 Influence of synthesis temperature and time on the gas permeation properties of microwave-derived silicalite-1 membranes (adapted from [81]) Fig. The gel layer first formed on the support after in situ aging. the support is contacted with a clear solution synthesis mixture. Then the membranes are put in a microwave oven for crystallization.0 2.

the separation behaviour of these new membranes is still poor. Recent TEM measurements have shown that the stacking of the nanoslabs is not perfect causing molecules to enter the membrane through the small mesopores between the nanoblocks [98]. a (H2/N2) > 1600. After drying and calcinations an extremely thin supported silicalite-1 membrane is obtained (Fig. In order to prevent intrusion of nanoblocks into the support pores. The structure of these precursor nanoparticles are still a controversial issue. Cross-section of a supported silicalite-1 membrane made by coating with nanoblocks [96]. There exist different concepts towards the generation of oriented pore systems [101]. the supports were first coated with one or two intermediate colloidal titania sol–gel layers decreasing the pore size to about 2–3 nm [97]. However. The recently reported combined UV and thermal treatment of spin-on silicalite-1 films could become a tool for the soft de-templating of the membrane with a reduced tendency of crack formation [99]. However. M. Coatings were made using a mixture of silicalite-1 nanoblocks and surfactants by dipcoating flat or tubular supports. A b-oriented MFI layer . Coatings were made on porous alumina supports with pore sizes of about 100 nm and 50–60 nm. the use of small-scale nanoblocks opens new perspective for the preparation of ultra-thin defect-free membranes. In the same way the stacking of small zeolite nanoblocks is believed to open a new approach for the preparation of a new type of zeolite membranes with potentially extreme thin top layers and extra high-flux [96]. 9. Zeolite LTA was dis- Fig. 10. catalytic membrane reactor. Typical for this new type of hierarchical materials is their bi-porosity containing not only the micropores inside the zeolitic nanoblocks. electrode. 11) composed of zeolitic nanoblocks possesses no 8-membered rings. The membranes show extremely high mixture separation factors of a (H2/CH4) > 1200. low dielectric constant material. Caro. Achieving an orientation of pores in films and membranes has been one of the challenging issues in the science of porous materials. but at the same time many small mesopores of a few nanometer in between the stacked nanoblocks.92]. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 Fig. the anisotropic pore structure of most zeolites requires the control of the membrane orientation.5. the best membranes have cut offs of 250 Dalton. Nevertheless. but very recent TEM measurements clearly show their silicalite-1 crystal structure [93]. protection or electrical insulation layer. that permeation through c-oriented MFI membranes is less favourable [102]. 2.220 J. From the study of the diffusion anisotropy of the MFI structure it can be expected. from the XRD it cannot be excluded that an amorphous alumosilicate gel has formed which blocks the pores of the Vycor glass. This leads to material properties that are deviating from the standard zeolite properties.4 nm3 [94]. 10). chemical sensor. nanoparticles smaller than 6 nm in the silicalite-1 clear solution and the further oriented aggregation of these precursors into bigger structures up to full crystal formation [91. The challenges consist in achieving a better stacking with sufficient adhesion to the porous support after removal of the surfactant molecule and in the intergrowth of the nanoblocks. solved in a short time in an HCl solution and spin-coated on a Vycor glass plate. Oriented zeolite membranes For the potential application of zeolite films as separation membrane.4 m3 (STP) m2 h1 bar1 at room temperature. Recently a very spectacular finding was published claiming a breakthrough in the use of nanoblocks [100]. These ‘‘nanoblocks” can be isolated and applied for powder preparation using the self-assembly properties of these nanoblocks supported by surfactants. In this way zeotiles or zeogrids can be formed [95]. and a (H2/CO) > 600 with acceptable fluxes of the order of 0. opto-electronic device. Illustration of the ‘‘in situ aging – microwave synthesis method” (after [88]). Older TEM and SAXS measurements had already elucidated the size and shape of these precursor particles: rectangular nanoblocks of 4  4  1. From different indication the authors conclude that their membrane (Fig.

and (iii) new applications by combination of zeolite layers with other membrane layers. Usually the nano-crystallites used as seeds do not show developed crystal faces and. To deposit the seeds in a b-orientation. It is interesting to note that in the latter case the separation factor increases with increasing temperature. Fig. If the crystal growth is anisotropic. to improve the quality of MFI membranes. the c-axis is the fastest growth direction. most MFI-membranes are c-oriented with a columnar structure (see. 3). The permeation experiments in [43] were carried out at very low loadings according to low integral xylene pressures p/ps  0. MFI membrane layers of different crystallographic orientation can be obtained but most often the MFI-type zeolite membranes show a crystallographic orientation of the c-axis of the zeolite layer perpendicular to the plane of the support surface [43. For MFI crystals usually the c-axis is the longest dimension and.110].5  0. the crystals with the fastest growth direction perpendicular to the plane of the membrane will dominate. After 36 h the gel layer was consumed and a single layer of b-oriented film was found. Whereas a two-step growth . Caro.221 J. By different analytic tools it was shown that the chitosan film adsorbed both TPAOH and TS-1 precursors resulting in a thin layer of TPAOH and TS-1 precursors on the surface. consequently.and trimers of tetrapropyl ammonium hydroxide (TPAOH) the growth of the b-oriented seeds in b-direction could be enhanced. Whereas a c-orientation results in a separation factor a  1. Tsapatsis and co-workers have prepared a b-oriented MFI silicalite-1 membrane [43]. 2.114]. b-orientation [111. The development of high-flux and high-selectivity MFI membranes for the xylene separation [43] shows the importance of a certain channel orientation and the significance of a seeded growth of an oriented particle monolayer. Therefore. Bi-layered zeolite membranes Different aims are followed when synthesizing multi-layer zeolite membranes: (i) improved separation selectivity by repeated crystallizations of one and the same zeolite type. 12). these crystallites are randomly oriented.5 m thick MFI films could be obtained by epitaxial growth starting from c-oriented seeds [104]. By comparison. e. 12 it becomes evident that one cannot identify a single superior microstructure for all separations.[103] oriented MFI membranes could be prepared successfully. Finally. Growing zeolite films from an oriented seed monolayer using secondary growth.[43] and a.108]. M. the b-orientation gives a xylene a  500 at 200 °C.% chitosan and acetic acid aqueous solution followed by a hydrothermal synthesis. The MFI seed monolayer was covalently attached to the intermediate silica layer by using 3-chloropropyl trimethoxy silane. Depending on the separation problem. the TS-1 film formed on the unmodified a-Al2O3 substrate was not continuous and randomly oriented [107]. while c-oriented hardly exhibit any selectivity for p-xylene (Fig. Now the mobile p-xylene can move more or less independently from the presence of o-xylene. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 a zeolite crystals aluminosilicate network acid solution b dissolution zeolite nano-blocks zeolitic pores coating 10 μ m porous support Fig. This situation changes dramatically at lower pore filling which is found at higher temperatures and/or lower partial pressures. b. From the separation patterns shown in Fig. those crystallites with their fastest growth direction pointing away from the seeded surface will grow more rapidly than crystallites in other orientations. Recently. By using di. 11. c-oriented 2. The corientation can be explained by the competitive growth model [108]. This finding is to be contrasted with the separation of n-/i-hydrocarbons (Fig. Recently. First.007 due to a high content of inert gas in the feed stream and the high temperature.2  0. This finding suggests that a more complex separation mechanism seems to take place with incorporation of selective grain boundaries. This experimental finding is characteristic of the interplay of adsorption and diffusion effects.112] or intermediate orientations [113. a certain microstructure performs better than others.g. the importance of the crystallographic layer orientation was addressed by Snyder and Tsaptatsis [8] (Fig.This Tsapatsis concept was further developed and highly boriented and intergrown MFI films could be produced by carrying out secondary growth of b-oriented seed layers under hydrothermal conditions using trimer tetrapropyl ammonium iodide as structure-directing agent (SDA) [105]. 12a). By this way. Schema of the preparation of zeolite nanoblocks by dissolving zeolite crystals in acid solution (a) and the cross-section of a resulting membrane obtained by spincoating this dissolved LTA crystals on a Vycor glass (b) [100]. Recently. is expected to exhibit higher fluxes.1 lm3) with developed crystal faces and attached the seeds as an b-oriented mono-seed layer to the support surface. The best separation performance for xylene isomers is obtained from b-oriented films. By the seeding of the support. 12b and c) in which c-oriented films are superior to b-oriented ones. Vroon proposed to repeat the crystallization step [124]. therefore. the orientation of the seed layer can be retained into the final membrane. The a-Al2O3 discs were first dip-coated with 2 wt. This very careful membrane preparation results in a superior separation performance which was demonstrated for the xylene isomers separation. The resulting polycrystalline films are 1 lm thin and consist of large b-oriented single crystals with straight channels running down the membrane thickness. b-Oriented MFI TS-1 films could be grown on chitosan-modified a-Al2O3 substrates [106]. Under certain growth conditions other crystallographic orientations were observed like a-orientation [109. Both in situ-growth as well as secondary growth can give different orientation of the zeolite layer. At low temperatures the zeolite pores are filled and the more mobile p-xylene cannot move faster through the pore network than the less mobile o-xylene. (ii) novel properties by combination of layers of different zeolite types. They used relative large seeds (0.6. the stainless steel support had to be smoothened by using an intermediate mesoporous silica layer.

9. The described FAU membrane was also successfully tested in alcohol/ ether separations. Two different tubular ZeoSepA membranes are produced: large size elements with 16 mm outer diameter and 1 m length for the de-watering of bio-ethanol and small size elements of 12 mm outer diameter and 0. respectively [140]. for the production of water-free ethanol.% ethanol.6).1 wt. bi-layered silicalite-1/ZSM-5 membranes were prepared and their permeation and separation properties were examined [134].(d) [119. Ltd. As an example. h0h-oriented () [121] and thin (0. the water flux at 75 °C is 3. Water separation As a blend for gasoline the water content of ethanol (EtOH) must be reduced to 2000 ppm. Membranes which combine a catalytically active zeolite layer with an inert one are interesting for membrane reactors [129–131]. The supports are in both cases porous a-alumina tubes.120]. As an example. India) 30. different zeolite structure types have been tried to prepare as a zeolite membrane applications. Mitsui-BNRI developed with the same supports used for the ZeoSepA element.% ethanol solution at 75 °C is about 7 kg m2 h1 with a separation factor a (water/ethanol)  10. Lai and Corcoran [130] patented the fabrication of multilayered zeolite membranes and demonstrated both seeded and epitaxial growth of ZSM-5 on silicalite-1 layers supported on porous alumina and stainless steel supports. Recently Mitsui declared that a new zeolite membrane plant for bio-alcohol de-hydration would be installed in Finland at the end of 2007 [141]. Caro. therefore. LTA membranes were developed and produced by BNRI (Bussan Nanotech Research Institute Inc. b. 12. Extremely high water fluxes are reported: 11. a second ZSM-5 layer (Bronsted acid sites. was found to be beneficial for the quality of MFI membranes. ANA. black: 200–400 °C [8]. OFF. hydrophilic) can be crystallized on the first one.% i-propanol.5– 3. From April to September 2003 Mitsui-BNRI tested successfully the de-watering of bio-ethanol in the pilot scale by using LTA membranes for vapour permeation in Piracicaba (Sao Paulo State. As the next step.65 wt. ethanol is separated from a . mostly MFI.8 m length for the recovering of i-propanol. The operating pressure and temperature of the membrane are 600 kPa and 130 °C.% ethanol and gave a water flux of 7– 10 kg m2 h1 and a separation factor a (water/ethanol)  300. The ethanol content in the permeate is below 0. M.6 and 22.000. Performance of c. Brazil). the product purity is 99.% water). a zeolite FAU membrane with lower Al-content (Si/Al between 1.7 kg m2 h1 with a separation factor a (water/i-propanol)  10.1.% water to 0.% ethanol and the product was 99. 14. Third. This FAU membrane was tested successfully in vapour permeation for the de-watering of a spent IPA solution with a starting content of 12 wt.t) [122. The capacity was 100 l/h working with a feed containing 93 wt. further repetitions of the crystallization step did not improve the membrane quality since as a result of the oxidative template removal crack formation was observed for increased membrane thickness. 3. 120 and 130 °C. 17.) which is a 100% subsidiary of Mitsui & Co.(j) [115–118].9 wt. 110. Mitsui-BNRI installed a larger steam permeation capacity at Daurala Sugar Works (Uttar Pradesh State. These hydrophilic LTA membranes have been applied in industry for de-hydration [136–139].5 lm) randomly (N. Bi-layered ZSM-5/silicalite-1 films were also prepared on non-porous quartz and silicon substrates by Li et al. For a 90%/10% i-propanol/water mixture. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 Fig. Multi-layered zeolite membranes with gradients of chemical composition or structure in the zeolite layers have the potential to expand the applications of zeolite membranes even further.%.123] oriented silicalite-1 layers at different temperatures. Therefore. FER.46 wt. MOR. Japan. The feed contains 93 wt. Further synthesis work seems to be necessary for successful preparations of bi-layered membranes. The hydrophilic LTA zeolite membrane is extremely selective in the separation of water from organic solutions by steam permeation and pervaporation and can be used.8 wt. Assuming that a mixture of the xylene isomers would be in contact with this bilayer membrane facing the Ti-modified silicalite-1 layer.5 and 1. Recently. CHA and ERI [125–128].222 J. for the ethyl tertiary butyl ether (ETBE) production the water content of (bio) ethanol must be <500 ppm. 12.000 l/d and a LTA membrane area of 30 m2. Case studies of mixture separation 3.9. Gora et al.000. The plant is in permanent operation since January 2004. gray: 100–200 °C. [133].%. The water flux of this membrane was evaluated at 75 °C in a pervaporation experiment with a model feed containing 90 wt. The water flux measured in pervaporation operation for 90 wt. for shapeselective oxidations a thin silicalite-1 layer was crystallized on an oxygen transporting perovskite membrane [135]. The smaller ZeoSepA membranes are mainly used for the recovery of i-propanol (IPA process) in the Japanese electronic industry using vapour permeation (azeotrope: 87. hydrophobic). The crystallization of shape-selective silicalite-1 layers on LTA and FAU layers turned out to be even more complicated [132]. LTA and FAU.4 kg m2 h1 at 100.1 wt. The colours indicate temperature regions: light gray: RT–100 °C. If the first layer on the support is silicalite-1 (shape-selective. but also BEA. mainly the p-xylene would enter the silicalite-1 layer and could become oxidized to the terephthalic acid with the oxygen released from the perovskite membrane.% bio-ethanol. [132] reported the seeded synthesis of silicalite-1 layers on top of zeolite LTA layers on porous Trumen supports by identifying conditions that allowed for the growth of the second layer without dissolution of the first. respectively. Second. there are ambitious attempts to combine zeolite layers with other inorganic membrane layers. The feed is evaporated by heating with steam.% ethanol.

All bio-ethanol samples could be de-watered to >99.% mixture of methanol/methyl tertiary butyl ether (MTBE) at 100 °C in vapour permeation.1 wt. The de-watering behaviour of these semi-industrially produced LTA membranes was tested by pervaporation with bio-ethanol feed stocks from real fermentation processes. Hermsdorf. In Europe the company inocermic GmbH. The impurities in the bio-ethanol from grain fermentation or wine production lowered the specific permeate flux by only 10–15% as compared to synthetic ethanol/water mixtures [147]. As a result. The membrane layer is inside an a-Al2O3 4-channel-support thus protected against mechanical damage. Hydrogen separation Gas polymer separation membranes are widely used for H2 recovery. mainly i-butane is adsorbed in the silicalite-1 pores thus blocking the diffusion of the rarely adsorbed highly mobile H2. SF6 has much lower gas permeance with activation energy larger than zero.5 Å).26 nm). M.265 nm were impermeable to N2 (0. Cu. In contrast to these X-ray amorphous metal oxide membranes. the full-silica composition provides a high stability against acids [152]. The pore size of 0. the X-ray amorphous metal oxide membranes. PHI and FAU membranes increases the stability but decreases the water fluxes due to a reduced hydrophilicity.5). With increasing temperature less i-butane is adsorbed and H2 can now diffuse in the resulting free volume [171]. Since the azeotrope i-propanol/water contains more water (12.55 nm pores of the silicalite-1 membrane due to their smaller kinetic diameter (0.2 by using USY6 seed crystals [143].% ethanol.151]. Organic solutions can be dried to water levels as low as 0. The narrow pore size zeolite structures and the rather compactness (low density of pores per unit area) of the suitable zeolite structures for H2 sieving require thin membrane layers for sufficient fluxes. only the sol–gel chemistry of SiO2 allows to form narrow pores but SiO2 is hydrothermally unstable.145]. In pervaporation tests of a 90/10 wt. Despite these developments in hydrophilic membrane separation. and zeolite membranes. In these cases the separation effect is based on the interplay of mixture adsorption and mixture diffusion effects. produces LTA membranes for de-watering processes.% ethanol [146]. However. methanol fluxes of 10 kg m2 h1 with selectivities a (methanol/MTBE) of 3000 are found [142]. carbon dioxide and SF6 through the silicalite membranes in a large temperature range.% H2O mixture a mixture separation factor a > 3.76 Å) < SF6 (5. At low temperature. The .29 nm and 0. 3. As an example. zeolite membranes can become important tools for H2 separation. in recent installations in Europe the adsorptive drying of ethanol was implemented instead of the membrane technology.4 wt.% i-propanol/water model mixture.190].% EtOH/10 wt. The preference of the molecular sieve adsorption process with zeolites for the dewatering of ethanol may be due to the fact that the azeotrope ethanol/water contains only a relative low amount of water (4. For a feed with 90 wt. ammonia 6 USY stands for ultrastable Y. resp.000 are found [146]. Parallel to these attempts on improvement of the commercial LTA membranes. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 5/95 wt.25 kg m2 h1 at 150 °C were obtained. the pore diameter should be larger than this but smaller than the kinetic diameter of the molecules from which H2 is to be separated.26 nm).3 nm as a thin supported layer.25 nm) and water (0. By the so called DELTA-T technology [148].% mixture of ethanol/ETBE with fluxes of 2. at 100–120°C water fluxes of 7–12 kg m2 h1 with separation factors H2O/EtOH > 1. An optimum between water flux and the concentration of silanols is found which is attributed to the trade-off between adsorption and diffusion [149]. mainly silica.%) so that the heat management of the cyclic adsorption processes can be managed. Germany.1 wt.1 kg m2 h1 with a (water/i-propanol)  690 were determined at 75 °C. ethanol is purified to less than 100 ppm water by using pelletized zeolite 3A.%). The stability of the hydrophilic FAU membranes could be increased having an Si/Al  2. Fig. by pervaporation and vapour permeation. Caro. Another promising way of the Delft group consists in the development of a H-SOD membrane with a thickness of about 2 lm on a-Al2O3 [150. The H-SOD membrane was tested for the pervaporative separation of water from i-propanol and pervaporation fluxes of 2. Y. by vapour permeation [142]. In general.50 nm. ZrO2. The membranes with a pore size of about 0. ZrO2 and TiO2 are more stable but their sol–gel chemistry does not allow to form narrow pore systems suitable for shape-selective gas separation.000 with water fluxes >0. Nb. first of all MFI are the most common ones. especially for bio-ethanol. 223 (0. The kinetic diameters increases as He (2.36 nm) and showed a small (due to the lack of defects) but remarkable permeance for small gases like He (0.1 kg m2 h1 and selectivities a (ethanol/ETBE) of 2800 and 1600 at 90 °C and 110 °C.5 wt. In addition to MFI (silicalite-1) membranes.% by pervaporation/steam permeation. most often prepared by a sol–gel technique using spin coating or dip coating.). A further increase of the stability of hydrophilic membranes was achieved by developing a weakly hydrophilic MFI-type membrane with Si/Al  120 [144. microporous membranes based on amorphous metal oxides SiO2 [159–162].6Å) < H2.29 nm.2. (2. Among the microporous membranes. respectively. which is a 100% subsidiary of HITK. crystalline zeolite membranes offer much better thermal and hydrothermal stability. A recently developed PHI membrane [153] shows after post-synthesis treatment of the membrane in the pervaporation of a 90 wt. hydrogen separation for silicalite-1 membranes have been reported in many studies [163–171]. Summarizing one can state that silicalite-1 as the only developed so far zeolite membrane can hardly compete with the other organic and inorganic membranes (Table 4). At room temperature. only have a very limited hydrothermal stability which excludes their use for H2 removal from atmospheres containing steam at high temperature. recent results recommend DDR membranes as tool for hydrogen separation [189.5 at room temperature to a  70 at 500 °C since both H2 and i-butane can pass the 0.36 nm  0. if it succeeds to develop narrow pore full SiO2 6-ring zeolite membranes for molecular sieving with pore sizes near 0. 13a) shows permeance of hydrogen. the mixture separation factor a of H2 from i-butane increases from about a  1.3 Å) < CO (3. For a 10/90 wt. V) are near to an use. By various techniques the Al-content of Y zeolites can be reduced to make them ultrastable.J. metal ones (Pd and its alloys with Ag. An interesting concept for the development of hydrophilic membranes consists in first incorporating a heteroatom like boron into the silicalite-1 framework and secondly in removing this heteroatom by thermal calcination. It can be even beneficial to use the more hydrophobic DDR membrane for water separation. TiO2. Gas permeation results incl. a lattice vacancy forms which is a nest of four hydroxyls that provides the de-borated silicalite-1 membrane hydrophilicity.89 Å) < CO2 (3. H2/SF6 permselectivity is 90. The substitution of the unstable towards hydrolysis LTA membrane by ZSM-5. USY is widely used as catalyst in FCC (fluid catalytic cracking). Since the kinetic diameter of H2 is around 0. Carbon molecular sieve (CMS) membranes form the third group [155– 158]. carbon monoxide.2 and 4. water fluxes of 3.44 nm guarantees a high water selectivity. much larger than the Knudsen selectivity (8.3 kg m2 h1 [154]. there are materials innovations in the development of novel hydrophilic zeolite membranes. As shown. helium. However. steam permeation using hydrophilic organic or inorganic membranes has a higher chance for realization in comparison with the ethanol/water mixture.

Different from the silicalite membrane.33 nm kinetic diameter.3–1.8–1.5 1000/T [ K-1] Fig. Caro. [189.%) Intermediate-temperature composite a Temperature [°C] Temperature [°C] b -7 200 -1 -2 100 25 H2 -1 Permeance [ mol·m ·s ·Pa ] -1 -2 -1 Permeance [ mol·m ·s ·Pa ] 10 500 400 300 He CO2 -8 10 CO Knudsen -9 10 1. 13b) shows permeance of various gases through small pore DDR zeolite membranes.d.2–0.97–0. The decrease in permeance with increasing temperature for carbon dioxide is mainly due to the decrease in equilibrium sorption constant with increasing temperature. H2O.1–3 (H2/n-butane) 4.0 1000/T [ K-1] 1.2–24.190].5 3. At high temperatures (>300 °C) and for small gas molecules.8–5.d.9–12. 40 35 1 21. 0.3 0. pervaporation selectivity of p-xylene to o-xylene for these silicalite membranes is larger than 20 [189.3 n.85 4 0.1 3 n.3 18. A few zeolite membranes have already shown promising results in the separation of CO2 from N2 and CH4 .1 0.03 n. Thus. Carbon dioxide can be strongly adsorbed by DDR zeolite. Further.190]. This kind of membrane failure would not happen with zeolite membranes.4 30–40 (H2/CO) Inf. the adsorption effect can be neglected and the gas permeance is determined by the diffusivity. the permeance decreases drastically with increasing temperature.1–16. the permeance for hydrogen and helium in the DDR zeolite membrane increases with increasing temperature exhibiting a large activation energy.0 3.000 4000–321 (H2/CH4) 54–132 (H2/CH4) 30–75 (H2/C3H8) 1.7–5.83 1 0.38 nm and N2 0. [173] [174] [175] [176] [177] [178] [179] [180] [181] [171] [182] [183] [184] [185] [186] 900 440 22 n. not the kinetic diameter of the molecules. CH4 0.5 50–500 5 0. Organic polymer Solid polymer electrolyte Thin-film Pd alloy membrane Molecular sieve silica <100 <100–200 300–450 200 100–300 450–550 20–200 65–290 30–210 500 80 22 25–150 35 677 0. 3. there exist polymer membranes with a high performance for CO2/CH4. 5. For carbon dioxide. 0.d. diffusion of hydrogen and helium in DDR zeolite has a larger activation energy than in silicalite. [187] [188] MFI seolite (silicalite-1) Molecular sieve carbon Single-phase ceramic mixed H+/e conductor (SCYb) Dual-phase mixed H+/e Conducting cermets Pd/YSZ (50 vol.224 J. Carbon dioxide separation Glassy polymer membranes are used for natural gas purification (removal of CO2. For silicalite membranes.5 2.05–0.6 P20 0.36 nm) [194]. H2S) but they suffer from swelling-induced plasticization by CO2 and hydrocarbons incorporation [193]. but these membranes have only a rather low separation performance in the CO2/N2 separation because of low diffusivity and solubility selectivities due to the similar size of CO2 and N2 (CO2 0. the permeance decreases with increasing temperature and is determined by the molecular weight. Diffusion of small molecules in the small pore DDR zeolite and amorphous silica membrane exhibits activated process. Fig.3 Inf. Data after Ref. M.0 2.d. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 Table 4 Typical performance of different H2-selective membranes [172] Membrane type T (°C) Thickness of the separation layer (lm) H2-flux at DpH2 = 2–1 bar 1 ðm3N m2 h Þ Separation factor (–) Ref.005 0. 13.4 2 1–2 2–6 10–25 4. with permeance decrease with increasing size of the molecules. Inf. Single gas permeance for silicalite membrane (a) prepared by template-free secondary growth method [191] and for DDR-type zeolite membrane made by NGK Insulators Ltd Japan [192] (b). The experimental data show that at high temperatures the molecules of these gases in the zeolite pores retain their gas characteristics.2 0.05–0.3.5 0.3 (H2/n-butane) 70 (H2/i-butane) 100–630 (H2/CH4) 331 (H2/N2) 400–50 (H2/CH4) 290 (H2/CH4) Inf.8 (H2/CO2) 0. 3.

215].6  108 mol m2 s1 Pa1 at 35 °C. CO2 selectivity of a DDR membrane for an equimolar CO2/CH4 mixture as function of permeation temperature [212]. 14). At a total pressure of 101 kPa and at 50 °C. O2/N2 (O). K+. are potentially good candidates as CO2selective membranes due to their desirable properties [214. 10 10 Selectivity / - [195–197]. Cu2+ cations in non-aqueous solutions increased both the CO2/ CH4 mixture selectivities by about 60%. 15). [210] found a mixture separation factor a = 400 with a CO2 permeance of P = 4. Ion exchange of H+-SAPO-34 membranes with Li+. Due to the fact that a CO2 separation will take place at elevated pressures. Separation of CO2 from air is found to range from 20 (100 °C) to 400 (50 °C) at 101 kPa total feed pressure. DDR membranes exhibit very high selectivities for CO2/CH4 separations with good permeances. Also hydrotalcites.38 nm) have pores that are similar in size to CH4 (0. Boron-ZSM-5 was found to have a higher selectivity towards CO2 than Na-ZSM-5 indicating that the adsorption mechanism includes electrostatic components. The CO2/H2 permeance ratio can be increased for MFI membranes by lowering the Si/Al ratio. The SAPO-34 membranes were synthesized on the inside of stainless steel tubes [219. Very recently the tuning of the CO2 permeation through SAPO34 by ion exchange was reported [221]. a CO2/CH4 mixture selectivity of a = 170 with a CO2 permeance of P = 1.222]. a CO2/N2 separation factor of 34. Na+.33 nm). that these membranes show high CO2/CH4 selectivities due to molecular sieving. The selectivity decreases with increasing feed pressure. Consequently DDR membranes show high CO2 flux and selectivity and an only negligible water influence on the separation performance in the CO2 separation from natural gas [220]. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 CO2 Selectivity / - 101 1000 500 1000 Total Feed Pressure / kPa 100 200 300 400 Temperature /K Fig. therefore.36 nm  0. Selectivities of equimolar mixtures through the DDR membrane as a function of the temperature constant total feed pressure of 101 kPa. Studies of single and binary permeation of CH4 and CO2 through silicalite-1 membranes gave that the CO2 selectivity in the permeation is due to the favourable CO2 adsorption [205].4 and a CO2/He separation factor of 12. The high selectivity is caused by the molecular sieving effect for CH4 and to some extend by the preferential adsorption of 10 10 10 4 3 2 1 0 200 300 400 T/K Fig. Air/Kr (d). For T-type (ERIOFF) membranes Cui et al. the selectivities were found to be low.4 were found [216]. Since the separation on these membranes is based on competitive adsorption.38 nm) but larger than CO2 (0. Most often the MFI type membrane was studied [198–202]. CO2. a CO2 permeance of 3. There are contradicting statements on the separability of CO2 from gas mixtures by zeolite membranes. On hydrotalcite membranes with a silicone top layer coated on their surface by vacuum suction. With decreasing temperatures the selectivity increases and at 21 °C a CO2/CH4 separation factor a = 560 was found. In contrast.2  107 mol m 2 s1 Pa1 was found at 22 °C. Recently. the same authors found that SAPO-34 membranes can separate CO2 from CH4 best at low temperatures with a selectivity of a = 270 at 20 °C [218]. in .15 had a slightly lower selectivity (a = 115) but a higher CO2 permeance (P = 4  107 mol m2 s1 Pa1) at 35 °C. 14. For a SAPO-34 membrane with a Si/Al gel ratio of 0.225 J. by ion exchange with Ba2+ or impregnation with calcium nitrate [207]. Caro. and SAPO-34 (0. N2O/Air (}). DDR (0. The SAPO-34 membranes effectively separate CO2 from CH4 for conditions at or near industrial requirements. 14. N2/CH4(s). CO2/Air (). At 7 MPa. The CO2/N2 selectivity was found to depend on (i) the kind of support and on (ii) modification of the MFI structure. Another praxis relevant separation problem is the CO2 removal from N2 in exhaust gases for CO2 sequestration. nicely illustrating its separation and permeation characteristics [213] (Figs. NHþ 4. Very powerful SAPO-34 membranes were recently synthesized by in situ–crystallization on a porous tubular stainless-steel support by Noble and Falconer [217].1. However. Tomita et al. SAPO34 membranes prepared with the higher Si/Al-ratio of 0. CO2 has a stronger electrostatic quadrupole moment than N2 leading to a preferential adsorption of CO2 from N2/CO2 mixtures [204].2–20 m3 (STP) m2 h1 bar1 on a NaY membrane was found with a mixture separation factor a = 20–50 [208. It can be expected. the CO2 permeation from pressurized feeds on a silicalite-1 membrane on different supports has been studied [206]. the mixture separation factors were found to be of the order of 60–90. [211] obtained a CO2/CH4 separation factor of a = 220 with a CO2 permeance of P = 7  108 mol m 2 s1 Pa1 at 28 °C on a DDR membrane. In a previous paper.44 nm). 15. Legend: CO2/CH4 (j). the SAPO-34 membrane showed a CO2/CH4 selectivity a = 100 for a 50/50% feed at room temperature over about a week [217] (Fig. 16). The selectivity drop with increasing pressure is attributed to the dependency of the diffusivity on the total loading. hydrophobic narrow pore zeolite membranes are more appropriate to separate CO2 from humid gases. After ion exchange. small-pore zeolites like zeolite T (ERI-OFF) (0. On FAU membranes for the separation of equimolar CO2/N2 mixtures at 40 °C. As an example. The CO2 selectivity drops with increasing temperature and pressure.41 nm por size). a layered double hydroxide compound. Therefore. but is still above 100 at 100 °C and 10 bar total feed pressure (Fig. M.209]. N2O/CO2 (N) [213]. sweep gas He at 101 kPa. A selectivity of about 10 was obtained for a silicalite-1 membrane at 120 °C [203]. the CO2 selectivity of an equimolar mixture was found to be >3000 [212]. a variety of mixture gas permeation results were published with an all-silica DDR membrane. CO2 flux and selectivity decrease in the presence of water since water has a strong affinity to the hydrophilic SAPO34 membrane [219]. A maximum mixture separation factor a (CO2/N2) = 12–13 was found between 6 and 16 bar total retentate pressure.

Fig.0. However. the same finding was made that the presence of water vapour significantly enhances the CO2 selectivity of an FAU membrane in the CO2/N2 mixture separation at 110–200 °C [226]. fractional crystallization. The membranes offer p-xylene permeances of about 2  107 mol m2 s1 Pa1 with a p-/o-xylene mixture separation factor a up to about 500.and m-xylenes (kinetic diameters about 0. Caro. J CO2 = 4.6. However. gas permeation test time for ZSM-5 zeolite membrane for moisture-saturated feed gases [225]. These MFI membranes were synthesized template-free with a random orientation of the crystals in the membrane layer. It is known that the separation factor of p-xylene decreases with increasing partial pressure [229. binary and multicomponent mixtures showing that the FAU membranes are CO2 selective The separation of the xylene isomers by.h-Oriented 27.Feed ¼ 30 kPa. In [43] it was shown that b-oriented silicalite-1 membranes give two orders of magnitude higher mixture separation factors in the p-/o-xylene separation in comparison with c-oriented films. Another. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 for dry feed gases over a wide range of temperatures and compositions. 17. This different experimental finding can be explained by the role of moisture. more simple explanation would be that CO2 is simply dissolved by a water film like in the case of a supported liquid film membrane. Xray amorphous silica membranes suffer from hydrothermal instability.h-Oriented h.9 11. e.4 m mol m2 s1) and CO2/N2 (a = 33.6 1. A silicalite-1 membrane was prepared by ‘‘Template-Free Secondary Growth on Two-Time Dip-Coated Supports” [231].2 24 32.3 9. the presence of water vapour in the feed enhances the CO2 flux significantly.137 kg m2 h1 which is explained by the absence of intercrystalline defect pores in the case of the template-free synthesis since no thermal template burning has to be applied. In a rather praxis-relevant study. The membranes can separate also CO2/CH4 (a = 22. [223] for equimolar mixtures CO2/N2 on FAU membranes the separation factor was determined to be a (CO2/N2)  2–5 at 30 °C whereas in [224] the opposite selectivity with a (N2/CO2)  5–8 was found. a (CO2/N2) in moisture-saturated feed gases is higher than that for the dry feed. These templated silica membranes exhibit ideal permselectivities for the p-/o-xylene separation of the order of 10–20 [228].3 to 0.68 nm) and to show a higher stability in comparison with silica. 17).6 nm. ‘‘Simple” silica membranes can be prepared by adding an organic template such as tetraethyl. good results for the separation of p-xylene from a multicomponent vapour mixture on tubular MFI Table 5 Single component pervaporation results of the xylene isomers on a MFI membrane at 25 °C [232] Orientation p-xylene flux (kg m2 h1) o-Xylene flux (kg m2 h1) Ideal p-/o-Xylene permselectivity Random c-Oriented c-Oriented h.1 6. 16. J CO2 = 3.9 at 100 °C and a increases as the permeation time increases [225] (Fig.4 nm can be shifted to a pore size of 0. Comparison of CO2/CH4 separation selectivity versus CO2 permeability (Robson plot) for polymeric membranes and two SAPO-34 membranes at room temperature and feed and permeate pressures of 222 and 84 kPa. However. which is 0. CO2/N2 separation factor vs.4.1 (60 °C.g. This experimental finding is explained by the mechanism that moisture occupies large pores through which N2 flows mainly and as a result. Outstanding separation behaviour was observed with a mixture separation factor a  40 and a p-xylene flux of 0.0. membranes with a preferred orientation showed comparable fluxes but decreased ideal permselectivities ranging only 2–3 in comparison with a random orientation giving a selectivity of 21 (Table 5) [232].226 J. respectively [217].6 3.9 9. The two arrows indicate the experimental results on two SAPO-34 membranes. a (CO2/N2)  54. On ZSM-5 zeolite membranes separation factors in favour of CO2 were found.1 22.3 at 25 °C and a (CO2/N2)  14. CO2 flux = 4 m mol m2 s1). The b-channel oriented zeolite membrane was obtained by a secondary growth method with b-oriented seed layer and using trimer-TPA as a template in the secondary growth step.5 21 3.8 .4.5–0. The role of water was also addressed in the permeation experiments using dry single-component. p-Xylene separation Fig.6 2.230]. PCO2 . Independently. M. In this light the separation of a liquid xylene mixture by pervaporation (that means operating at saturation loading) represents a challenging task.4 2.55 nm should be perfectly suited to separate the p-xylene (kinetic diameter 0. 3.% in He. This finding indicates that the microstructure strongly affects the ability of the membrane to perform xylene separation. adsorption or distillation are energy consuming operations that should be replaced by membrane separation. A crystalline silicalite-1 membrane with a pore size of about 0.1% of its saturated vapour pressure at 200 °C).6 m mol m2 s1 [227]. the usual pore size of silica membranes from 0.9 35. The maximum CO2/H2 mixture separation factor a was 19.58 nm) from the bulkier o. However these tests were carried out under extremely low xylene partial pressures (2 vol.or tetrapropyl ammonium bromide to polymeric silica sols.

3. M. Innovative applications 4.8 to 1. 18. Fig. There are different ways to increase the yield of an esterification. As hydrogen was removed selectively through the silicalite-1 membrane.3.55 nm pores due to their kinetic diameters (0. after an oxidative regeneration the activity and selectivity are restored completely. An opposite target can be the continuous removal of ethanol from the fermentation broth since the fermentation process stops at ethanol concentrations near 15 wt. In the pervaporation of a 10 wt. However.% ethanol) could be increased from 0. Membrane reactors There are numerous examples for the application of zeolite membranes to enhance a chemical reaction like de-hydrogenation. reducing the membrane thickness and increasing the Si/Al of the MFI membrane the ethanol fluxes should be increased. by selective coating of a pre-shaped Co/SiO2 catalyst pellet by a HZSM-5 shell thus enhancing the selectivity for middle i-paraffins and suppressing the formation of long-chain hydrocarbons in the Fischer–Tropsch process [243]. The same membranes can be used to separate more polar alcohols from less polar ones or from organics. In a first example. respectively. the ethanol enriched flux (between 70 and 80 wt. Caro. 18). The online repairing of the membrane by deposition and carbonization of 1. From an eight-component mixture of xylene isomers and other hydrocarbons a mixture separation factor a (p-xylene/m. In the case of the low-temperature esterification of methanol or ethanol with short chain monovalent hydrocarbon acids. Typical fluxes are of the order of about 1 kg m2 h1 with 85 wt. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 227 Table 6 Comparison of the separation behaviour of different membranes for synthetic mixtures of 5/95 wt.% MTBE mixture at 50 °C a mixture separation factor a > 10. Further. In the conventional packed-bed experiment the thermodynamic equilibrium conversion was obtained (Fig. In particular the FAU membrane was successfully tested in alcohols separation [234]. Despite the fact that both H2 and i-butane can pass the 0. Most frequently the cheapest educt is present in a surplus concentration or the low boiling ester is removed by reactive distillation. PTMSPa ZSM-5 (Si/Ge  40) Silicalite-1 ZSM-5 (Si/Al  300) – Steel Steel 30 nm TiO2 250 nm TiO2 30 30 30 40 40 0. By changing the top layer of the support from a 5 nm c-Al2O3 ultra filtration layer to a 250 nm a-Al2O3 micro filtration layer.7 with a p-xylene flux of 6.% ethanol/water the mixture separation factor 127 and a total flux of 0. zeolite films can enhance as well the selectivity of reactions.000 with methanol fluxes of about 1. By optimizing the support structure. Conditions: WHSV = 1 h1. the i-butane conversion increased by about 15% [171]. Recently TS-1 membranes have been evaluated in the ethanol separation and in a pervaporation test for a feed containing 5 wt. thus increasing the conversion and the yield of a de-hydration or an de-hydrogenation.77 kg m2 h1 were found [237].1.plus o-xylene) of 7. zeolite membranes recommend themselves as an ‘‘membrane extractor reactor” removing under equilibrium controlled reaction kinetics conditions small product molecules like hydrogen or water. coking is promoted and after approximately 2 h time-onstream the olefin yield of the membrane reactor drops below that of the classical packed-bed [247].g. However. respectively).50 nm.%.% ethanol which corresponds to a separation factor of 57.% methanol/90 wt. the interplay of mixture adsorption and mixture diffusion results in a H2-selectivity at high temperatures and in an i-butane selectivity of the silicalite-1 membrane at low temperatures. to support esterifications at higher temperatures.J. Therefore. membranes have been obtained [233]. Another concept is to keep the concentration of the product water as low as possible by the use of adsorbents like LTA zeolites or even by chemical reactions like the hydrolysis of Al tri-isopropylate thus consuming water.5 kg m2 h1 were determined [235].g.33 0.74 1. because of the hydrogen removal.68 0. However. A second example deals with the water removal during an esterification. 4.29 nm and 0. data after 20 min time on stream [171]. Alcohol separation Several types of hydrophilic membranes like LTA and FAU can be used for water extraction. hydrophilic organic polymer membranes can be used for the in situ de-watering in a membrane reactor. Hydrophobic membranes such as the MFI type are in development to solve this problem (Table 6). e. partial oxidation.% ethanol/water [236] Membrane Support T (°C) Flux (kg m2 h1) a (EtOH/H2O) Ref.% ethanol from a feed with 8 wt. by [244–247].39 19 47 32 73 48 [238] [239] [240] [241] a Poly(trimethyl silyl propyne). Increase of the i-butane conversion above the equilibrium limit if hydrogen is removed through a silicalite-1 membrane.4 kg m2 h1 [236]. The traditional applications of zeolite membranes in reactors is focused on conversion enhancement by equilibrium displacement or by selectively removing reaction rate inhibitors [242]. Cr2O3/Al2O3-catalyst (Süd-Chemie).22 0.8  106 mol m2 s1 was found at 250 °C and atmospheric feed pressure. The removal of hydrogen leads to hydrogen-depleted conditions which have two positive effects: (i) the conversion of i-butane is increased due to a lower rate of the reverse reaction and (ii) the selectivity to i-butene is increased because the hydrogenolysis is suppressed. Due to their molecular sieve properties. hydrophilic inorganic membranes with high stability against .5. Experimental results for the silicalite-1 assisted de-hydrogenation of i-butane were described. isomerization or esterification. membrane area per unit mass of catalyst = 20 cm2 g1. at the beginning of the reaction the i-butene yield in the membrane reactor is higher by about 1/3 than in the conventional packed-bed. e. a MFI zeolite membrane is used in the catalytic de-hydrogenations of i-butane. The relative low ethanol fluxes are due to the test conditions with real fermentation broths.5-triisopropylbenzene can reduce the nanoscale intercrystalline defect pores to enhance the separation factor.

Micro membrane reactor Fig. A recent example of fine chemical reaction carried out in a membrane micro reactor is the Knoevenagel condensation reaction where the selective removal of the by-product water during the reaction led to a 25% improvement in the conversion [264]. consequently. This means Fig. and top view SEM pictures of (1) the 3-lm thick CsNaX catalyst powder deposited on the micro channel wall and (2) the 6-lm thick NaA grown on the back of the stainless steel plate on the right. the ester yield can be increased from 52% to 92% by removal of water through the membrane (Fig. Vapour permeation is also applicable to the in situ removal of water in the formation of unsaturated polyesters [248]. even at water feed concentrations below 1. (a) Membrane micro reactor design [264. The benefits of a membrane supported esterification was shown for the reaction of n-propanol with propionic acid using a ZSM-5 membrane of the Si/ Al = 96. the all-silica DDR membrane turns out to be well suited to separate water from organic solvents under pervaporation conditions [249. lowered kinetic inhibition. 19). Caro. The combination of the concepts of membrane reactor and process miniaturization provides new routes for chemical synthesis that promises to be more efficient.% ethanol mixture with water fluxes >0. All the water produced by the reaction was completely removed and the membrane was operating below its capacity [266]. 19. . Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 strong acids have to be used. and top view SEM pictures of the micro channel (top-left) and the (1) 3-lm thick CsNaX film grown on top of the (2) 6. The in situ-water removal by a sol–gel silica-based membrane [252] and a ceramic supported polymer membrane [253] in presence of a CO/CO2-shift active Fe-based catalyst resulted in increased total carbon conversion to hydrocarbons. Water could also be removed from methanol/ethanol/water mixtures. 20. almost complete conversion of about 100% was reached within 8 h in the esterification of lactic acid with ethanol [248]. M. on site and on demand production network for high value added products in the form of miniature factories and micro-pharmacies [257].265] on the left. etc. This ZSM-5 membrane of Si/Al = 96 is acid stable up to pH 1 but – due to the low Al-contents – the hydrophilicity is low and. In the Fischer–Tropsch synthesis the removal of the by-product water has several advantages on the reactor performance such as reduced catalyst de-activation.3 kg m2 h1 seems to be the better choice [154]. 20a) [265].256]. cleaner and safer [255. These smart integrated micro chemical systems are expected to bring into realization a distributed. A recently developed PHI membrane with a mixture separation factor a > 3000 for a 10 wt. while the organic molecules experience increasing diffusion hindrance with increasing size. it was proposed to use hydrophilic membranes to increase reactor productivity [251]. Therefore.5-lm thick NaA membrane in the micro channel bottom-left. Despite it’s hydrophobic character.5% [250]. ZSM-5 type zeolite membranes are suitable candidates to fulfil these demands. the resulting water flux of 72 g m2 h1 bar1 is still much too low for technical applications.2. For infinite reaction time.250]. This water removal is attributed to molecular sieving.% water/90 wt. The reaction between benzaldehyde and ethyl cyanoacetate to produce ethyl-2-cyano-3-phenylacrylate was catalyzed by a CsNaX zeolite catalyst deposited on the micro channel and the water was selectively pervaporated across a LTA membrane (Fig. Excellent performance in dewatering ethanol (flux = 2 kg m2 h1 and a = 1500) is observed and the membrane is also able to selectively remove water from methanol (flux = 5 kg m2 h1 and a = 9). Water easily passes through the DDR structure. Conventionally. (b) Membrane reactor design on the left.228 J. In another application for the selective removal of water by pervaporation and vapour permeation during an esterification by using hydrophilic ZSM-5 and MOR membranes. hydrophilic membranes are used for dehydration of solvents. Simulated conversion enhancement by water removal via a hydrophilic ZSM-5 membrane with an Si/Al = 96 in a membrane reactor for the esterification reaction propionic acid + i-propanol ? ester + water at 70 °C [136]. The application of more hydrophilic zeolite membranes than silica or organic polymers with higher selectivity and higher water fluxes such as LTA [254] and H-SOD [150] for the in situ water removal in Fischer–Tropsch synthesis looks promising. 4. The incorporation of zeolites in micro reactors as functional elements including catalysts [258–260] and membranes have been reported in previous works [261–263].

but beyond 67 °C. Zeolite nano-crystals can be coated on substrates to form a transparent film with about 20 nm surface roughness. one can shift the reflection minimum to achieve a neutral colour [282]. Zeolite membranes could also be reformed into micro needles for transdermal drug delivery. In this method. Parallel. post-treatment method during the removal of the organic template in combination with a thermal treatment. acceptable heat conductivity and low dielectric constant. The nanospheres were then prepared in situ using ferrocene as catalyst and the silicon substrate as silica source. In this 229 Fig. FE-SEM image of an a-. Synthesis of advanced materials was also successfully carried out in zeolite membrane enclosed micro channels [271]. 20b). A silicon wafer is coated with 1 M TPAOH and then zeolite films were crystallized under steam by adding some water to the autoclave. UV radiation decreases drastically the quantity of silanols.and b-out-of-plane orientation were obtained in a temperature window from 100 to 200 °C (Fig.b-oriented silicalite-1 film obtained by steaming a SDA-oxidized silicon wafer [277]. S. An improvement in the product yield and selectivity towards azoxybenzene was also observed.270]. The vapour phase can be only steam or a mixture of steam and a structure-directing agent (SDA) such as TPAOH. Increasing temperature was beneficial for both yield and selectivity. As an alternative method for crystallizing a zeolite layer in the liquid phase. A multichannel membrane micro reactor for continuous selective oxidation of aniline by hydrogen peroxide on TS-1 nanoparticles was successfully demonstrated. The resulting coating showed a broadband anti-reflection effect with less than 1% average reflection over the visible range. the silicon wafer serves both as support of the grown zeolite film and as the Si source for the formation of the silicalite-1 film. The as-synthesized SDA-containing MFI films are non-porous and allow the coating of complex shapes and in confined spaces by in situ-crystallization [284].e. Last but not least. which reduces the effect of catalyst de-activation during the reaction. Controlled drug delivery was achieved through the permeable zeolite wall. The high surface area to volume ratio that can be attained in the micro reactor (3000 m2/ m3) facilitates the selective removal of water by-product. as electrode. Caro. methylation of the silica surface is obtained by decomposition and reaction of the TPA ions as SDA. With proper control of the film thickness. M.J. by the so-called dry gel conversion a dry (alumino) silicate gel can be converted into a zeolite layer in the presence of vapours [275]. Zeolite membrane hollow spheres prepared by growing a thin zeolite shell on polymer beads were used to store and release bioactive molecules for studying cell signalling [281]. that is to say that both thermodynamic and mass transfer constraints were removed. The zeolite micro channels were fabricated by selective etching of the silicon below the zeolite membrane to create the membrane-enclosed micro channels.4. zeolite layers can act as functional film in chemical sensors. Noack / Microporous and Mesoporous Materials 115 (2008) 215–233 that the performance of the membrane micro reactor is limited mainly by the kinetics. high-silica zeolite coating on metals and metal alloys can be a promising technology for corrosion protection of metals [283]. In contrast to the conventional steam-assisted crystallization [276] in which the substrate is coated with all the nutrients and then steam-treated. By this method. 21). 4. as opto-electronic device or low dielectric constant material. hydrophobicity.3. 4. Mixed matrix membranes Soon after the first preparation of synthetic zeolites the idea was born to incorporate zeolite crystals as modifier into a polymer matrix thus using the easy processing of polymers [285–287]. the oxidized surface layer of a silicon wafer can be transformed into an silicalite-1 zeolite film [277. hydrophilic antimicrobial coatings [273] or sulfonated zeolite BEA for proton exchange membranes [274]. The hollow silica nanospheres were successfully prepared within the zeolite-enclosed microchannels by a ship-in-a-bottle approach. This broadband neutral colour antireflection coating was achieved in a single step sol–gel process and can find application in the display industry. Porous pure-silica materials are attractive as insulator material in on-chip interconnects due to their high porosity. 21. From the selective removal of the by-product water in the membrane micro reactors also benefited other Knoevenagel condensation reactions such as reactions between benzaldehyde and (1) ethyl acetoacetate (EAA) and (2) diethyl malonate (DEM) [268]. A remarkable improvement could be achieved by the UV treatment of spin-on silicalite-1 films to induce hydrophobization [99]. A fourfold increase in reaction conversion was obtained when the improved CsNaX– NH2 catalyst was used instead of CsNaX [267]. Mixed matrix membranes are interesting systems to enhance the . scrofa domesticus) without damage [280]. Functional films In addition to its use as separation membrane and catalytic membrane reactor. micro reactor operation was ineffective due to bubble formation and hydrogen peroxide decomposition [269. Locating the separation membrane immediately next to the catalyst further improved the membrane micro reactor performance (Fig. Pure silcalite-1 films with preferential a. the formation of cracks during the removal of the organic template is minimized. Azobenzene was obtained as by-product and its formation was attributed to homogeneous reaction of nitrosobenzene with aniline. Pure-silica zeolites have a remarkably higher mechanical strength and hydrophobicity than amorphous porous silicas due to their crystalline structure making them a likely dielectric material for enabling smaller feature sizes in future generation of microprocessors [279].278]. by a novel steam-assisted method. The intergrown zeolites provided excellent mechanical strength and could pierce through skin (i. This method seems to be very useful for zeolite film applications as chemical sensor or for optoelectronics. as protection or insulation layer. as corrosion-resistant coatings [272].

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