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Journal of Membrane Science 316 (2008) 3–17

Review

Microwave synthesis of zeolite membranes: A review
Yanshuo Li, Weishen Yang ∗
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Received 2 July 2007; received in revised form 28 August 2007; accepted 31 August 2007
Available online 14 September 2007

Abstract
Significant progress has been achieved in the last years on microwave synthesis of zeolite membranes. In many cases, microwave synthesis has
proven to remarkably reduce the synthesis time. In addition, microwave synthesis could also result in different membrane morphology, orientation,
composition, and thus the different permeation characteristics as compared with those synthesized by conventional heating. This review attempts to
summarize the obtained progress in microwave synthesis of zeolite membranes. Some topics are discussed, including: (1) case study of microwave
synthesis of zeolite membranes, e.g. LTA, MFI, AFI, and other types of zeolite membranes; (2) differences between conventional and microwave
synthesis; (3) formation mechanism and the so called “specific microwave effect” in the case of microwave synthesis of zeolite membranes; (4)
scaling-up of zeolite membrane production by employing microwave heating. The latter three topics are mainly focused on LTA type zeolite
membranes. Concluding remarks and future perspective are also suggested in the end.
© 2007 Elsevier B.V. All rights reserved.
Keywords: LTA; MFI; AFI; Zeolite membrane; Microwave synthesis; Non-thermal effect

Contents
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Brief introduction of microwave-assisted synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Basic physical principles of microwaves and microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Advantages of microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Specific microwave effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microwave synthesis of zeolite membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. LTA (NaA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. MFI (ZSM-5 and Silicalite-1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. AFI (AlPO4 -5 and SAPO-5) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4. Others (SOD, FAU and ETS-4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Comparison between microwave heating and conventional heating synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Formation mechanism of zeolite membranes under microwave irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal and non-thermal effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Scaling-up of zeolite membrane production by adopting microwave heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding remarks and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction

Corresponding author. Tel.: +86 411 84379073; fax: +86 411 84694447.
E-mail address: Yangws@dicp.ac.cn (W. Yang).
URL: http://yanggroup.dicp.ac.cn (W. Yang).

0376-7388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2007.08.054

Since the mid of 1990s, owing to the potential molecular sieving action, controlled host–guest interactions and high thermal
and chemical stability, the preparations, characterizations and

The accumulated number of published articles on microwave-assisted synthesis of zeolites and zeolite membranes (Scopus search). Since then. and some review articles were published which are well worth reading [19–27].15] have provided extensive coverage of this subject. Yang / Journal of Membrane Science 316 (2008) 3–17 Fig. there has been a steadily growing interest in microwave synthesis of zeolite membranes (Fig. and operate in a frequency range between 0. ionic. and interfacial (space-charge) polarization. dipolar molecules try to orient themselves or be in phase with the field. Beginning with a brief introduction of microwave and microwaveassisted synthesis. Li. applications of membranes. heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientific community. The pioneer work on microwave synthesis of zeolite can be traced to 1988. Based on the results obtained in our laboratory. including electronic. A large number of review articles [1–13] and several book chapters [14. all the reported microwave chemistry experiments are currently conducted at 2450 MHz (the corresponding wavelength is 12. their motion is restricted by resisting forces (inter-particle interaction and . This present review attempts to summarize the obtained progress in microwave synthesis of zeolite membranes. In the last years. Mingos and co-workers [26] have given a thorough explanation of the underlying theory of microwave dielectric heating. the number of publications began to increase year by year. Finally. the comparison between conventional and microwave synthesis and the “specific microwave effect” will be discussed. 2. microwave-assisted synthesis (especially microwave assistant organic synthesis) has matured into a highly useful technique. the above-cited reviews are recommended. Mobil researchers claimed the microwave synthesis of microporous zeolites. special attention is given to the microwave synthesis of LTA type zeolite membranes. molecular (dipole). and so in the fields of zeolite and zeolite membranes. 2. They have wavelengths between 0. it can be described that in the presence of an oscillating field. In the following section. There are several mechanisms which are responsible for this. the so far reported literatures on microwave synthesis of zeolite membranes will then be summarized. In a US patent. 1). Another probable reason is that 2450 MHz magnetrons are mostly often used in the available commercial microwave chemistry equipments. To our knowledge.3 and 30 GHz. Nuchter et al. Caro and co-workers reported the synthesis of large AlPO4 -5 single crystals by microwave heating.1. The first published article on microwave synthesis of zeolite appeared in 1993. One reason is that near to this frequency. and microwave engineers. Basic physical principles of microwaves and microwave heating Microwaves lie in the electromagnetic spectrum between infrared waves and radio waves. in which Jansen and co-workers reported that microwave-assisted crystallization of Y-type and ZSM-5 zeolite could be finished in a much shorter synthesis time and free of undesired phase as compared with conventional heating [17]. 1). 1. the microwave energy absorption by liquid water is maximal. However. mixed oxides and mesoporous molecular sieves by employing microwave energy. Tompsett et al.01 and 1 m. films and coatings of zeolite and zeolite-like materials (in short called “zeolite membranes” in this review) have been extensively investigated. [20] dedicated a comprehensive review on the microwave synthesis of nanoporous materials and summarized the preparation of zeolites. Furthermore. For more general information on the subject of microwave chemistry. especially after the mid-1990s (Fig. a membrane with one-dimensional pore structure could be obtained [18]. Interaction of dielectric materials with microwaves leads to what is generally described as dielectric heating due to a net polarization of the substance. Cundy produced an excellent review on the microwave synthesis and modification of zeolites [19].24 cm). For easier understanding. Brief introduction of microwave-assisted synthesis After several years of joint efforts of the chemists. an outlook on the future development of microwave synthesis of zeolite membranes will be given. In 1998. [22] have given a critical technology overview and focused mostly on reaction engineering in microwave field. After then. By embedding these AlPO4 -5 crystals in a Ni grid. In 1995. material scientists. we will briefly describe the basic physical principles of microwave chemistry to the membranologists who are not familiar with this subject. The typical bands for industrial applications are 915 ± 15 and 2450 ± 50 MHz. W. Recently.4 Y. such as zeolite NaA and ZSM-5 [16].

microwave synthesized membranes maintained high separation factor even when water content was lower than 1% H2 /n-C4 H10 permselectivity was 11. held for 5–40 min Seeded Gel: 3:1:2:200. the permeance of the microwave synthesized zeolite membrane was increased by four times. and then microwave synthesis at 90 ◦ C for 25 min Alumina In situ 5:1:50:1000. crystallizing (15–25 min) and dissolving (>25 min) The membrane formed on the ␥-Al2 O3 /␣-Al2 O3 substrate had a higher gas permeance The membrane synthesized in sol had higher permeance than that in gel Aging the gel favored the formation of NaA membranes in short time. the thickness of the membranes could be controlled by varying the amount of the reaction mixture In situ aging time.85:3. Na2 O/SiO2 /Al2 O3 /H2 O Fluxed at 90 ◦ C for 25 min Alumina In situ 1:0. Yang / Journal of Membrane Science 316 (2008) 3–17 Substrate a Not reported.R.R. CH: aging at 50 ◦ C for 7 h in oven. N.0:200. high alkalinity and sodium cation concentration disfavored the formation of membranes H2 /N2 selectivity increased with increasing synthesis time. microwave synthesized membrane was thinner than the one synthesized by conventional heating The synthesis time was greatly reduced while permeance enhanced compared with conventional heating synthesis. and then microwave synthesis at 90 ◦ C for 25 min. Na2 O/SiO2 /Al2 O3 /H2 O Fluxed at 90 ◦ C for 4–25 min ␥-Al2 O3 modified ␣-Al2 O3 and ␣-Al2 O3 Alumina Seeded Alumina Seeded 3:2:1:150.66 × 10−6 mol m−2 s−1 Pa−1 . W. and then conventional synthesis at 90 ◦ C for 3h Heated to 90 ◦ C in 60 s. held for 15 min Main results Membrane Performances Microwave oven type Reference On Cu substrates a dense film was formed. but on stainless steel no layer-like zeolite film was formed Four stage under microwave radiation: absorbing (0–15 min).5 × 10−8 mol s−1 m−2 Pa−1 N.a Goldstar Er-4010 [68] H2 /C3 H8 permselectivity was 6.60 and 9.Table 1 LTA zeolite membranes from microwave synthesis Synthesis strategy Synthesis Composition Preparation procedure Copper and silicon wafer In situ 3:1:2:200.64 × 10−6 mol s−1 m−2 Pa−1 Modified domestic microwave oven [75] N. Na2 O/Al2 O3 /SiO2 /H2 O Heated to 90 ◦ C in 60 s. H2 permeance was 21 × 10−7 mol m−2 s−1 Pa−1 Modified domestic microwave oven [83] Modified domestic microwave oven [81] Microwave heating increased the reaction rate greatly. nucleation.8.8. while keeping comparable permselectivity Microwave heating greatly accelerated the zeolite membrane formation. respectively. and then microwave synthesis at 90 ◦ C for 0–35 min Alumina In situ 5:1:50:1000. HR-8801MHaier [64] For H2 O/IPA pervaporation. H2 permeance was 51. LTA zeolite membranes with few non-zeolite pores can be synthesized by using microwave heating The synthesis time was 8–12 times shorter than conventional heating. in situ aging was necessary for microwave synthesis of LTA zeolite membranes without seeding The formation process of LTA membranes under microwave field was comprehensively studied. Na2 O/Al2 O3 /SiO2 /H2 O 120 ◦ C for 1 min followed by 100 ◦ C for 30–240 min Alumina Seeded 3:1:2:200. temperature and microwave heating time have influence on the membrane quality. respectively O2 /N2 and H2 /n-C4 H10 permselectivities were 1.R. H2 permeance was 213 × 10−8 mol m−2 s−1 Pa−1 HR-8801M Haier [65] Modified domestic microwave oven [84] Permeance of O2 and N2 were 0. Li. HR-8801MHaier [66] N. Na2 O/Al2 O3 /SiO2 /H2 O MH: aging at 50 ◦ C for 7 h in oven.R. SiO2 /Al2 O3 /Na2 O/H2 O Alumina Seeded 50:1:5:1000. [86] H2 /N2 and H2 /C3 H8 permselectivities were 5. Na2 O/Al2 O3 /SiO2 /H2 O Heated to 90 ◦ C in 60 s. Na2 O/Al2 O3 /SiO2 /H2 O Heated to 90 ◦ C in 1 min.97. NN-K580MFS P = 100 W [77] H2 /N2 selectivity was 3. SiO2 /Al2 O3 /Na2 O/H2 O 3–6:2:1:150. SiO2 /Al2 O3 /Na2 O/H2 O Aging at 50 ◦ C for 7 h in oven. held for 15 min Alumina Seeded 50:1:5:1000.02 and 11. held for 15 min Alumina Seeded 50:1:5:1000. Na2 O/Al2 O3 /SiO2 /H2 O Heated to 90 ◦ C in 1 min. respectively.68 and 0. held for 5–45 min Sol: 5:1:50:1000. the formation mechanism of LTA zeolite membranes was proposed Compared with conventional heating. SiO2 /Al2 O3 /Na2 O/H2 O Aging at 50 ◦ C for 7 h in air oven. Al2 O3 /SiO2 /Na2 O/H2 O Synthesis in microwave oven at 250 W for 15–20 min. 5 . NN-K580MFS P = 100 W [79] N.R. dried in microwave oven at 120 W for 10 min Alumina In situ 5:1:50:1000.23 at 25 ◦ C Modified domestic microwave oven [104] Highest H2 permeance was 2.17. multi-stage synthesis resulted in the formation of more impurity phase Y.

In order to further improve the permeance and permselectivity of zeolite NaA membranes. Our initial idea is to take the advantages of fast microwave synthesis to shorten the zeolite crystallization time so as to reduce the membrane thickness and to improve the flux. or Fermi–Dirac). tan δ). FAU. typified by bulk metals and alloys. in 1999 [86]. e. Afterward. Maxwell–Boltzmann. while keeping comparable permselectivity for H2 /n-C4 H10 [81. It was reported that the thickness of the membranes could be controlled by varying the amount of the reaction mixture. time-averaged drift motion of matter (or both). which restrict their motion and generate heat. (2) materials that are transparent to microwaves.43. 2. and ETS-4 types of zeolite membranes have been successfully synthesized by microwave heating.63–70] and microwave assistant secondary growth [55. Generally. several glasses. molecules. Table 1 summarizes the microwave synthesis conditions and main experimental results of LTA zeolite membranes. (4) it can realize selective heating because chemicals and the containment materials for chemical reactions do not interact equally with microwaves. or electrons) where the kinetic energy statistics of such fluctuations are represented by a single thermodynamic equilibrium distribution (i. atoms. the efforts to synthesize of NaA zeolite membranes started in the late 1990s. Microwave heating greatly accelerated the crystallization rate and reduced the synthesis time to 10 min. microwave dielectric heating has the following advantages for chemical synthesis (thermal effects of microwave): (1) the introduction of microwave energy into a chemical reaction can lead to much higher heating rates than those which are achieved conventionally. typified by fused quartz. According to the explanation of Booske et al. (2) the microwave energy is introduced into the chemical reactor remotely without direct contact between the energy source and the reacting chemicals. and Kuhnert has given a highlight to discuss the non-thermal microwave effect in organic synthesis [32]. Advantages of microwave heating Commonly used strategies for zeolite membrane synthesis can be classified into three categories: in situ hydrothermal synthesis [33–45]. pre-seeding the support with microwave synthesized NaA zeolite was needed to overcome the nucleation-related bottleneck [87.6 Y. the synthesis time was shortened by 8–12 times by using microwave heating. concluded that all the speculations on special and nonthermal effects in microwave heating has no basis when taking into account the increased temperatures caused by super-heating or concentration effects [21]. which leads to the concepts of non-thermal effects. even the energy of hydrogen bond is several tens of Joules per mole). Bose–Einstein. This section is intended to be a comprehensive collection of these reports although accidental omission is inevitable. also called “specific microwave effect”. and vapor phase transport synthesis [58–62]. In a previ- 3. Teflon. “Non-thermal” effects refer to interactions resulting in nonequilibrium energy fluctuation distributions or deterministic. Microwave synthesis of zeolite membranes 3. Kappe. which can be described best as local overheating and is comparable to the delayed boiling of overheated liquids under conventional conditions. NaA zeolite membranes were microwave synthesized on alumina support by Han et al. it should be pointed out that the energy of microwave photon (≈1 J/mol) is far too small to break typical chemical bands (usually >300 J/mol.3. Microwave techniques combining with these strategies could create some novel synthesis routes. ous review. ions. etc.g. MFI. LTA type zeolite membranes are most extensively studied in microwave synthesis of zeolite membrane research. Conventional heating (i. “thermal” refers to interactions resulting in increased random motion of particles (e. [30] published an excellent review on the synthetic results to which the microwave effect has been attributed. The microwave absorption ability of a material is directly proportional to its dissipation factor.1. Yang / Journal of Membrane Science 316 (2008) 3–17 electric resistance). and (3) materials that absorb microwaves which constitute the most important class of materials for microwave synthesis. among which.e. [29] suggested the so-called “specific microwave effect”. this topic is still a controversial matter and open to interpretation.2. aqueous solution. is used to predict materials behavior in a microwave field. Compared with conventional heating. e. especially solid-state reactions. and the permeance of the membrane was increased by 4 times. Compared with conventional heating. conduction. 2. W. LTA (NaA) Due to the relative simple synthesis gel/solution (containing no templates) and low crystallization temperature (usually <100 ◦ C). [28].. (5) “hot spots” yielded on local boundaries by reflections and refractions may result in a “super-heating” effect. however. we considered modifying the . LTA.46–57]. Jacob et al. SOD. a ratio of the dielectric loss (loss factor) to the dielectric constant.e. AFI. No separation data was reported for this membrane. Dissipation factor (often called the loss tangent. Specific microwave effect Firstly. ceramics. Here. could not be interpreted by thermal effects of microwave solely. polar solvent.g. This indicates that the membrane was formed by physical deposition of crystals from the bulk onto the support. etc. secondary (seeded) growth synthesis [41.84].88]. 2.71–85] have been reported for membrane preparation. Li. the numerous experimental observations on reaction rate enhancement in microwave field. However. copper.83. as illustrated in Fig. Nevertheless. convection.g. (3) it is volumetric and instantaneous (or rapid) heating with no wall or heat diffusion effects. In our group. materials can be classified into three categories based on their interaction with microwaves: (1) materials that reflect microwaves. and heat radiation) has a heat source on the outside and relies on transferring the heat to the surface of the material and then conducting the heat to the middle of the material. in situ microwave synthesis [18. Langa et al. Loupy and Perreux [31] published a tentative rationalization of non-thermal effects in organic synthesis.

SiO2 /TPAOH/H2 O/EtOH Crystallization temperature: 120–180 ◦ C.Table 2 MFI zeolite membranes from microwave synthesis Substrate Synthesis strategy Synthesis Composition Preparation procedure In situ 1:0. while c-orientation at 180 ◦ C MFI zeolite membranes with a (1 0 1) preferred orientation were prepared at 160 ◦ C for 2 h. duration: 3–40 min Heated at full power for 2–15 min. with the increment of the dielectric constants. Calcinated at 550 ◦ C or ozone treated at 200 ◦ C a Membrane performances Microwave oven type Reference The crystal exhibited the same shape and orientation regardless of the nature of the under coatings. increasing the microwave heating time produced denser and smaller zeolite crystals. the same selectivity but lower permeance was obtained for the ozone activated membrane ETHOS 1600. SharpR-10R P = 50 W [93] N. calcinated at 600 ◦ C for 2 h Alumina Seeded 25:3:1500:100. duration: 30–150 min Calcinated at 450 ◦ C for 4 h Alumina Seeded 25:3:1500:100. Milestone.A. three methods were used to eliminate the template: ozone treatment at 160 ◦ C for 1. SiO2 /(TPA)2 O/H2 O Cordierite honeycomb substrates and alumina disks In situ 100:10:1800. Domestic microwave oven. Milestone. Pmax = 400 W [71] Y. P = 800 W [73] Membrane with higher n/i-butane selectivity (40–50) and medium permeance was synthesized at higher temperature (160 ◦ C) ETHOS 1600. Pmax = 400 W [72] The ideal selectivity for n/i-C4H10 lies in the range 47–50 at 20–50 ◦ C. (1 0 1) oriented membrane was synthesized at 160 ◦ C.2 ◦ C/min). SiO2 /TPAOH/H2 O Rapid heating and cooling. SiO2 /TPAOH/H2 O/EtOH Crystallization temperature: 160 ◦ C. the surface coverage increased Microwave heating favored a great control over the temperature profile After 10 min microwave heating and 6 h hydrothermal synthesis.5 h. and calcination with a rapid heating rate (5 ◦ C/min) N. membrane with 74 ␮m thickness was obtained. W. increasing microwave power produced smaller numbers of larger crystals Microwave synthesis was a promising method for the rapid synthesis of MFI membranes with relatively high permeance and selectivity.2:22 or 100. temperature: 135–200 ◦ C. 7 .5:1:675. duration: 30–150 min.a MARS-5 CEM P = 600 W [113] N. Yang / Journal of Membrane Science 316 (2008) 3–17 WO3 /TiO2 /Fe2 O3 /SiO2 coated glass Main results Not reported. and then hydrothermal synthesis at 150 ◦ C for 3–24 h. calcinated in air at 500 ◦ C Silicon wafer In situ 6. Li. calcination with a slow heating rate (0.A. TEOS/TPAOH/H2 O Heated for 90 min at 150 ◦ C.A.

This convenient and effective method has made the mass production of LTA zeolite membranes a reality. 3. and the permselectivity for H2 /n-C4 H10 was also increased to some extent [75]. The morphology. which were achieved by the consequential crystallization under fast and homogeneous microwave heating. macroporous alumina support with a thin mesoporous top-layer to prevent the penetration of the reagent into the support. This aspect will be discussed in Section 7. The second step is the nucleation and crystals growth on the support. These crystals could be . [83]). Combining microwave heating with secondary growth strategy. AFI (AlPO4 -5 and SAPO-5) In 1995. Recently. 2. W. thickness. synthesized Silicalite-1 zeolite membranes on alumina supports with (1 0 1) and (0 0 1) preferred orientation [72]. Films containing oriented 100 nm Silicalite-1 crystals have been in situ synthesized on a silicon wafer using rapid heating and cooling [93]. This is probable due to the relative high temperature (usually >150 ◦ C) for MFI zeolite crystallization and the fast degradation of the TPA+ template under microwave conditions [19]. [18] reported the microwave synthesis of large AlPO4 -5 single crystals. NaA zeolite crystals could inter-grow together in a short time. the articles published on microwave synthesis of MFI type zeolite membranes are limited. which were obtained by in situ aging. Table 2 summarizes the microwave synthesis conditions and main experimental results of MFI type zeolite membranes. Secondary growth strategy was also adopted by them. Comparative synthesis model of zeolite membrane by microwave heating and conventional heating (redrawn from Ref. they developed an ultra-rapid and reproducible synthesis method for thin and good quality MFI membranes by coupling the microwave-assisted synthesis with a rapid template removal method (ozone treatment) [71]. but silica-alumina gel instead of clear solution was used for zeolite crystallization.79.6 were successfully microwave synthesized without seeding by this method [64. crystal preferential orientation (CPO) and single gas permeation properties of the Silicalite-1 membranes have been studied in relation to the synthesis parameters. Yang / Journal of Membrane Science 316 (2008) 3–17 Fig.89]. Motuzas et al. Cheng et al. MFI (ZSM-5 and Silicalite-1) Although the largest amount of work has been done on membranes with the framework topology of MFI (ZSM-5 and Silicalite-1).66]. Because artificial seeding was replaced by in situ heterogeneous nucleation.81. It was reported that the high alkalinity and sodium cation concentration disfavored the growth of membranes [77]. Microwave synthesis of Silicalite-1 zeolite membranes was reported by Koegler et al. Li. 3. homogeneity.2. The H2 permeance was increased by 1.3 times. also carried out the investigation on microwave synthesis of A-type zeolite membranes [77. Recently. The obtained result coincided with our assumption.8 Y. The first step is the rearrangement of synthesis mixture and the formation of germ nuclei on the support surface. a new method called “in-situ aging-microwave heating” method was developed for zeolite membrane synthesis by our group. a much higher nucleation rate favored by microwave heating greatly enhanced the number of nuclei on the support surface. This method decouples two successive steps in the formation of zeolite membranes. High quality NaA zeolite membranes with H2 /N2 permselectivity of 5.3. The ideal selectivity for n/i-C4 H10 was in the range 40–50.90–92]. and defect-free LTA zeolite membranes were thus formed. Caro et al. As a result. LTA zeolite membranes with excellent pervaporation performance were also prepared with high reproducibility.5–3. In our previous investigation and most of the other researchers’ study. it was found that surface seeding is necessary to promote the formation of NaA zeolite membranes and suppress the formation of impurity phases [54.

CEM [85] N. ultrasonicated.7–1.5 N.5:50:1000 or Al2 O3 /SiO2 /Na2 O/H2 O Heated to 90 ◦ C in 60 s and held for 15–45 min. ultrasonicated.8 and layer thicknesses in the range of 0.33:761. multi-stage synthesis Reaction temperature: 160–200 ◦ C.5–2 × 10−8 mol m−2 s−1 Pa−1 . and size of the AlPO4 -5 crystals could be controlled by experimental conditions. Questron [69] Morphology. microwave heating induced heterogeneous nucleation in the pore systems of anodized alumina substrate The degree of c-orientation and zeolite coverage varied with experimental conditions Separation factor: n-butane/triisopropyl-benzene = 1220.4.A. n-heptane/toluene = 0.3:2. Qwave 3000. duration: 1–10 min.3:425. involving seeds prepared by microwave heating. Pmax = 1200 W [18] N. MDS 2000. NaOH/TiO2 /SiO2 /H2 O/H2 O2 (pH 12.a MLS 1200 MLS GmbH Leutkirch [80] MARSX-press CEM [74] Y. Na2 O/Al2 O3 /SiO2 /H2 O SOD In situ and seeded 1:5:50:1000 or 1:0. microwave heating led to homogenous film growth and microporosity a Not reported. meanwhile it could curb the formation of impurity phase H2 /n-C4 H10 permselectivity >1000. highest selectivity was 6.45:2. Yang / Journal of Membrane Science 316 (2008) 3–17 Substrate a Not reported. W. oriented membrane showed excellent selectivity based on the molecular size c-Oriented growth of AlPO4 -5 was obtained by microwave heating. calcinated in oxygen at 350 ◦ C over night Main results Membrane performances Microwave oven type Reference Microwave greatly accelerated the formation of AlPO4 -5 zeolite without any impurity.8 MLS1200. was used to synthesize larger area and homogeneous SOD membranes with good reproducibility Dense inter-grown FAU layers with Si/Al ratios of 1. n-heptane/triethylbeneze = 105.1) Pulse laser deposition was used for surface seeding. Al2 O3 /SiO2 /Na2 O/H2 O Reacted at 120 ◦ C for 2 h. 9 .32:0. reacted at 235 ◦ C for 20–60 min Main results Membrane performances Microwave oven type Reference Microwave heating not only promoted the formation of SOD membrane but also inhibited the formation of impurity The pre-seeding/secondary growth method. microwave power: 300–1000 W.3:0. CEM [114] N.7. n-eptane/mesitylene = 1.5 min.4:1.3:425:6.4:1.3:8.8–6 ␮m were obtained. CH4 /CO2 permselectivity was 3.85:3:200 or 1:3. Al2 O3 /P2 O5 /TEA/HF/H2 O/iC3 H7 OH Heated to 180 ◦ C for 60 s Anodized alumina Seeded 1:1.3:425.28–1. duration: 15–180 min FAU Seeded 1:10:14:840. washed and dried at 90 ◦ C for 1h Reaction temperature: 90–150 ◦ C.A. permeance of H2 was 1.A.6:1.1–0. Al2 O3 /P2 O3 /TEA/HF/H2 O Heated at 180 ◦ C. repeated twice ETS-4 Seeded 16:1:11.a MDS 2000.5.A.3:1. N2 /CO2 permselectivity was 8. Al2 O3 /P2 O3 /TEOS/TEA/HF/H2O Gold coated quartz crystal microbalances (QCM) Seeded 1:1. microwave heating resulted in a higher Si/Al ratios of the membrane Microwave heating greatly accelerated the reaction rate. washed and dried at 90 ◦ C for 1 h Anodic Alumina Seeded 1:1.14 × 10−7 mol m−2 s−1 Pa−1 N2 and He permeances were typically in the range 0.Table 3 AFI zeolite membranes from microwave synthesis Synthesis strategy Synthesis Composition Preparation procedure Ni grid Seeded 1:1. orientation. Li.2 Modified domestic microwave oven [76] ETHOS 1600 Milestone P = 250 W [67] Permeance order: H2 > CH4 > N2 > O2 > CO2 > nC4 H10 > SF6 at 23 ◦ C. FAU and ETS-4 zeolite membranes from microwave synthesis Membrane type Synthesis strategy Synthesis Composition Preparation procedure SOD In situ 50:1:5:1000.5–4. Table 4 SOD. Al2 O3 /P2 O5 /(TEA)2 O/H2 O Heated at 185 ◦ C for 2.0:50–900.3–1.

3. The effects of various synthesis parameters on the degree of preferred orientation along the c-crystal axis of the AFI structure and the zeolite coverage on alumina support were discussed. which allowed the synthesis of larger and homogeneous samples with a good reproducibility. a LTA zeolite membrane synthesized by conventional heating is composed of well-shaped cubic LTA crystals. Weh et al. bundles of layered crystals form the tightly packed membrane. microwave heating time. Our recent progress in the in situ microwave synthesis of zeolite membranes (“in-situ aging-microwave heating” method [66]) improved the membrane selectivity remarkable (permselectivity for H2 /N2 was 5. and recently it was successfully synthesized as a membrane form by pulsed laser deposition (for seeding) and microwave treatment (for secondary growth) [74]. i. The temperature. [69] used microwave heating to prepare thin films of AlPO4 -5 on gold coated quartz crystal microbalances (QCMs). the authors developed another indirect strategy.e. In the case of zeolite membranes. Julbe et al.10 Y. FAU and ETS-4) Some other types of zeolite membranes have also been synthesized by adopting microwave heating. 3.4 to 1. Microwave irradiation shortened the synthesis time considerably as compared to conventional heating. as shown in Table 1. For examples. In our researches on microwave synthesis of LTA type zeolite membranes. In order to overcome this problem. A pure hydroxy-sodalite zeolite membrane was easily synthesized by microwave heating method. it has been shown that compared with conventional heating. In this section. Films prepared by conventional heating showed no crystal orientation. 4. the as-synthesized FAU type zeolite membrane had a slightly increased Si/Al ratio (from 1.99–102].8). Table 3 summarizes the microwave synthesis conditions and main experimental results of AFI type zeolite membranes. either conventional heating or microwave heating. Tsai et al. Under continuous microwave irradiation.84]. Our initial researches on microwave synthesis of zeolite membranes mainly focused on how to reduce synthesis time and improve the membrane permeance by introducing microwave heating technique. W. microwave heating can remarkably reduce synthesis time. Li. was usually synthesized by conventional heating method. We have also successfully synthesized high quality pure hydroxy-sodalite zeolite membranes on ␣-Al2 O3 support by a microwave-assisted in situ crystallization method [76]. We attributed this to the distinctive morphology of microwave synthesized LTA zeolite membranes (sphere grains with undefined crystal facets) from that of conventional heating synthesized . In our study. which consisted of NaX zeolite. Comparison between microwave heating and conventional heating synthesis In the above section. Besides this morphological difference. we will mainly discuss the differences in membrane characteristic and performance of the membranes synthesized by microwave heating and conventional heating.80–82. and aging time affected the thickness and orientation of the zeolite crystals. They found that the dissolution of the ␣-alumina support revealed a disturbing phenomenon for both the reproducibility and scaling-up of the direct membrane synthesis. Although NaA zeolite membranes synthesized by microwave heating in short time usually had high permeance. Our recent studies found that microwave assistant hydrothermal synthesis can be an efficient tool for the morphology control of LTA type zeolite membranes. Weh et al. The pure hydroxy-sodalite zeolite membrane synthesized by microwave heating method was found to be well inter-grown. [67] have evaluated the potential of microwave heating for synthesizing sodalite membranes on tubular supports. Yang / Journal of Membrane Science 316 (2008) 3–17 formed in as little time as 60 s. synthesized composite membranes that consisted of thin faujasite layers on the surfaces of porous ␥-Al2 O3 support disks by using a two-step synthesis (seeded growth) method [80]. which is higher than the common value of NaA zeolite [64–66]. however. This is one of the most frequently mentioned advantages of microwave synthesis. phase selectivity [98]. more than eight times faster than by the conventional hydrothermal synthesis method. it has been reported that the microwave synthesis method could provide an efficient way to control particle size distribution [94–97]. which resulted in the rapid synthesis of ETS-4 in less than 1 h compared to 36–48 h for the traditional synthesis. it was interesting to find that the as-synthesized NaA zeolite membrane had a Si/Al ratio of 1. while the membrane synthesized under pulsing microwave irradiation consists of sphere grains without well-developed crystal faces.60) while maintained the membrane permeance high. we have also found that microwave heating is favorable for the synthesis of the high silica analogue of FAU type zeolite membranes. [85] prepared well-aligned SAPO-5 membrane using microwave heating on an anodized aluminum substrate.43 as determined by XPS characterization.4. Engelhard titanosilicate (ETS-4) has octahedral coordination in addition to tetrahedral coordination. while a zeolite membrane. microwave synthesis can also lead to a compositional difference of the synthesized zeolite membranes. The gas permeation results showed that the H2 /N2 permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. As shown in Fig. Various sets of samples with different silicon contents in reactant gels and different reaction times in secondary microwave hydrothermal heating were studied. Y-type zeolite membranes. [80] reported that when using microwave heating instead of conventional heating. the permselectivity of the membranes was not very high (permselectivity for H2 /N2 was just around the Kundsen diffusion ratio). NaA zeolite and hydroxy-sodalite zeolite. microwave synthesis also leads to different membrane characteristics from those synthesized by conventional heating [64–66. Two different kinds of heating were used in the secondary growth step. and were found to be ideal for one-dimensional molecular sieving. the pre-seeding/secondary growth method. and macroscopic morphology [96. power. Only 45 min was needed by this method. as summarized in Table 4. Others (SOD. Mintova et al. In the synthesis of porous materials.

3. one (well-shaped cubic crystals) (see Fig.Y. and the formation of sphere grains with undefined crystal facets was necessary to achieve a pinhole-free continuous zeolite layer [103]. When WF was 1. Yang / Journal of Membrane Science 316 (2008) 3–17 11 Fig. and at the same point.%. In our studies on FAU type zeolite membranes. W. when WF broke through 2.0 wt. with the permeation flux decreasing approximately linearly from 0.0 to 90.86 to 0. The compactness difference between microwave heating and conventional heating synthesized NaA zeolite membranes was also confirmed by pervaporation separation test [65].0 wt.0 wt.%. Li. This indicated that the membrane synthesized by conventional heating might have quite a few non-zeolitic pores (in nano-size). the pervaporation selectivity of Ytype zeolite membranes for ethanol/water were increased from 60 to more than 300 by using microwave heating. WP was only 18. 4. the permeate flux abnormally increased dramatically. When WF was low.g. which leaded to a decrease in WP and increase in permeate flux.%.2 wt. Comparison of pervaporation performances between NaA zeolite membranes synthesized by microwave heating and conventional heating. 5. e. As for the membrane synthesized by microwave heating (Fig. the ever-occurring triangularly shaped gap between growing crystals on the support would lead to the systematic imperfections of the synthesized membranes.0 wt. . as the water concentration in feed (WF ) decreased from 9. Wp: the water concentration in permeate. for the membrane synthesized by conventional heating. The quality difference between microwave heating synthesized membranes and conventional heating synthesized ones through the same strategy should be due to the different heating mechanism between microwave heating and conventional heating. thus much isopropanol began to pass through the pores. the water concentration in permeate (WP ) varied from 100. the study on microwave synthesis of zeolite membranes is still at the initial stage.08 kg m−2 h−1 .6 to 0. and the optimization of zeolite Fig. WP decreased rapidly. As pointed out by Mcleary and Jansen. 4). we also found that microwave heating could be an effective tool to improve membrane compactness. However. SEM images of conventional heating and microwave (both pulsed and continuous) heating synthesized NaA zeolite membranes. 3).%. the adsorbed water were not enough to block the defects to inhibit isopropanol permeation. Formation mechanism of zeolite membranes under microwave irradiation Up to now.%.

the amorphous particles transform into LTA crystal particles with the same size.106]. and then the synthesis system was transferred to a conventional oven. XPS. 5. This propagation growth process is accompanied by the agglomeration and densification of the primary particles. Thermal and non-thermal effects In order to distinguish between the“thermal effect” and the “non-thermal effect” in the synthesis of the NaA zeolite membranes by microwave heating. it can be concluded that the function of microwave irradiation during zeolite membrane formation is mainly derived from its thermal effect. Therefore. Based on the above results and referred to the reported formation mechanism of LTA zeolite [105. but the relevant reports on the formation mechanism rather rare. With this mechanism. A seeded support was placed in the synthesis mixture and heated up quickly to 90 ◦ C in a microwave oven. 6. a gel layer is first formed on the support after in situ aging. XRD. a fundamental understanding of the formation mechanisms of zeolite membranes is of great significance. This observation is in accordance with Zah et al. and the formation mechanism of LTA zeolite membranes was proposed [64]. . these pre-nuclei rapidly and simultaneously develop into crystal nuclei. in our previous study [81]. Recently. which contains plenty of prenuclei. it is still suspected that there will be some specific microwave effects. which was preheated to 90 ◦ C. as illustrated in Fig. SEM. Therefore.’s latest report on the formation mechanism of conventional heating synthesized LTA zeolite membranes [107]. 5. it is believed that the essential mechanism of zeolite formation is similar what ever in powder form or membrane form. ATR/FTIR. and gas permeation to characterize the whole formation process of LTA zeolite membranes which were synthesized by “in-situ aging-microwave heating” method. During the following microwave assistant crystallization. which is low effective and difficult to be generalized. We have once tried to preliminarily characterize the formation mechanisms of microwave synthesized LTA zeolite membranes under the existence of zeolite seeds (secondary growth method) [81. W. Li.12 Y. compact LTA zeolite membranes consisting of spherical grains with undefined crystal facets are obtained. the following experiment was designed. membrane synthesis is still a trial-and-error procedure. we adopted gravimetric analysis. In this way. However. [63]). and finally. and then crystal growth by propagation through the amorphous primary particles (with size of ca. Schematic illustration of the proposed formation mechanism of NaA type zeolite membrane synthesized by an “in-situ aging-microwave heating” method (after Ref.104]. and this will be discussed in the following section. Yang / Journal of Membrane Science 316 (2008) 3–17 Fig. 50 nm) goes on.

The acceleration effect of microwave synthesis is mainly due to its thermal effects. which enhances the agglomeration of these particles. Non-thermal effects: (1) electric double layer structures of the primary particles are destroyed through Maxwell–Wagner polarization mechanism. we concluded that the fast formation of NaA zeolite membranes by microwave was mainly promoted by the “non-thermal effect” [81]. which hastens the densification between agglomerated particles. Microwave heating is a promising solution to solve this problem. In addition. temperature profiles and control within the synthesis autoclave are necessary. the thermal and non-thermal effects of microwaves during “in-situ aging-microwave heating” synthesis are speculated as bellow: Thermal effects: (1) selective heating. whereas. This proposal is referred to the reports of Hwang et al. energy is supplied by an electromagnetic field directly to the material. After 15 min of synthesis.e. In microwave processing. This indicates that the existence of non-thermal effects can not be completely ruled out. the as-synthesized membrane was characterized by XRD. Li. [110. it was found that the linear growth rate of NaA zeolite under microwave field was at the same level as under conventional heating conditions. the uniformity of the microwave field (multi-mode applicators) can be . Based on the comparison of the conventional heating synthesis and microwave heating synthesis. W. and thus the density gradients caused by sedimentation under the gravity field will not be significant any longer. It was observed that there is no significant difference in the intensity of the diffraction patterns of NaA zeolite between the as-synthesized membrane and the seeded support. (3) the Si O (Al O ) bonds on the surface of the primary particles are selectively activated by microwaves. This results in a rapid heating throughout the material with reduced thermal gradients. [100] and Blanco et al. The intensity of the diffraction patterns of NaA zeolite of the as-synthesized membrane is much smaller than that of the NaA zeolite membrane synthesized by microwave heating of 15 min. the extraordinary morphology of the microwave synthesized LTA zeolite membranes is mainly a result of the non-thermal effects of microwave synthesis. we have investigated the preparation of NaA zeolite membranes with different pulse lengths of microwave irradiation. On the other hand. which increases the reaction rate in the gel phase. microwaves selectively couple with the gel layer because the gel phase has a higher dissipation factor (tan ␦). which results in a simultaneous nucleation and synchronous propagation of crystallization. This indicates that microwave does not enhance the crystallization kinetics of NaA zeolite. Thus. the gel layer is heated quickly and entirely and homogeneously. Recently. 7. Different from what we have concluded before [80]. 6. Pilot scale vapor permeation dewatering installation with 0. It was found that the optimal synthesis time for compact membranes (evaluated by pervaporation tests) was determined by the total microwave irradiation time and not by the total heating time. i.8 m2 membrane area. and the acceleration effect of microwave synthesis is mainly a result of fast and simultaneous nucleation. (2) volumetric heating. (2) the H-bonds are destroyed under microwave irradiation. This coincides with the “active water” concept proposed by Jansen et al. i. a more elaborately designed experiment was carried out to further investigate the microwave effect in the synthesis of NaA zeolite membranes by “in-situ aging-microwave heating” method [108].e.Y.111]. [109]. combined with some qualitative theoretical analysis. Yang / Journal of Membrane Science 316 (2008) 3–17 13 Fig. Scaling-up of zeolite membrane production by adopting microwave heating To overcome the thermal gradients and density gradients that occurred in large-scale membrane production. Volumetric heating can also reduce processing times.

% water. microwave syn- thesis could also result in different membrane morphology. K. and the so-called specific microwave effect (although there is still controversy). In terms of industrial production. LTA. 90 (2006) 198–220. [2] T. as pointed by Conner et al. including thermal and non-thermal effects. Li.3 wt. “selective activation”. Environ. volumetric and instantaneous (or rapid) heating. Application of zeolite membranes. each module is made up of 7 NaA zeolite membrane tubes. Therefore. Chiang.E. Caro. and to scale-up membrane production. Bein. inhibiting the formation of impurity is another main advantage of microwave synthesis. R. 6. such as “active water”. Porous Mater. Due to the very high water selectivity of microwave synthesized NaA zeolite membranes. Mater. which can be seen as a milestone in the development of microwave synthesis of zeolite membranes. Phys. the reactor engineering must be considered in order to understand and control microwave synthesis. The separation unit consists of four modules with a total permeation area of about 0. Kolsch. P. which has been observed by many researches in numerous cases. e. pressure swing adsorption and polymeric membranes.S. Based on the data obtained on this installation. Solids 62 (2001) 1899–1910. [5] F. it is still in the early stages of development. scaling-up of NaA zeolite membrane has been achieved in our group. and thus in different permeation characteristics as compared with conventional heating synthesized ones. Membranes and films of zeolite and zeolite-like materials. This installation produces 225 L/D fuel ethanol containing less than 0. 2003CB615802). Zeolite membranes—state of their development and perspective.D. Combining hydrothermal synthesis and microwave heating technique. fast and energy-saving microwave heating can lower the fabrication cost and make the continuous production possible. 8. 38 (2000) 3–24. non-equilibrium thermodynamics and molecular dynamics. McLeary. Synthesis and applications of molecular sieve layers and membranes. taking the advantage of microwave volumetric heating. Long term stability test (>1500 h. Acknowledgements This work was supported by the Ministry of Science and Technology of China (Grant No.% water from the bio-ethanol with 10 wt. First of all. Attempts have been made to understand the formation mechanism of zeolite membranes under microwave irradiation.14 Y. Comparison between microwave heating and conventional heating has been performed preliminarily.T. [6] T. Microporous Mesoporous Mater. 8 (1996) 1636–1653. orientation. However. still carrying on now) showed that microwave synthesized NaA zeolite membranes provide very good stability in vapor permeation. Sci. 245 (2004) 1–33. J. in order to understand the formation mechanism and to provide generalized guidance for the microwave synthesis of zeolite membranes. [112]. microwave synthesis is especially suitable for mass production of large-area zeolite membranes. W. Zeolite based films. membranes and membrane reactors: progress and prospects. This has already been realized in the case of NaA zeolite membranes in our group. Yang / Journal of Membrane Science 316 (2008) 3–17 improved by increasing the size of the oven cavity. it is calculated that the energy consumption of zeolite membrane based vapor permeation dewatering process is much smaller than that of azeotropic distillation. MFI. composition. Membr. J. are the basis for understanding the real function of microwave irradiation in synthesis. to increase the synthesis reproducibility. In addition. Chem.L. F. M. microwave synthesis of zeolite membranes is especially promising for industrial production.g. [4] J. Jansen. Bundled synthesis of hollow fiber supported zeolite membranes. R. physical chemistry and microwave engineering. Chao. Therefore. SOD. Significant progress has been achieved in the past several years on microwave synthesis of zeolite membranes. etc. Concluding remarks and future perspective Microwave synthesis is a promising method for the fast synthesis of zeolite membranes. Noble.2 MPa. in situ characterization of the changes in chemistry and physics (energy transfer) are required. AFI. it was found that the essential mechanism of zeolite formation is similar. it was concluded that the function of microwave irradiation during zeolite membrane formation is mainly derived from its thermal effect. BP and Youth Science Fund of DICP (No. As for LTA zeolite membranes. Schafer. Due to the unique features of microwave heating. especially in the case of LTA type zeolite membranes.8 m2 . A pilot scale vapor permeation dewatering installation based on NaA zeolite membranes has been set up recently. FAU and ETS-4 types of zeolite membranes have been reported to be successfully synthesized under the irradiation of microwaves.C. it is still suspected that there will be some specific microwave effects. Noack. Kapteijn.’s review [20]). Chem. Scaling-up microwave synthesis of FAU type zeolite membranes is ongoing in our group now. Besides remarkably accelerating the zeolite membrane formation. Microporous Mesoporous Mater. specific and selective heating. a 5000 tonnes per year organic dewatering plant and a reaction-separation integrated unit based on NaA zeolite membrane (microwave synthesized) are in construction. [3] A. .C.J. ethanol recovery of >99. Fundamentals and applications of pervaporation through zeolite membranes. It was found that besides the often mentioned microwave accelerating effect. J. as shown in Fig. reaction acceleration effect. Bowen. Falconer.8% was obtained. films and coatings. References [1] E. are planned to be carried out in the near future. and further research is required to expand the research area. e. Comprehensive characterization of the chemical and physical changes during microwave synthesis and in-depth theoretical analysis. such as neutron and X-ray scattering. Now. S200609). Friendly Processes 125 (1999) 1–12. This needs the interdisciplinary cooperation among material science. J. whether under microwave or conventional heating conditions. and vibrational spectroscopy (refer to Tompsett et al. Mizukami. to improve the membrane performance. The vapor permeation process is operated at 110 ◦ C and 0. Nevertheless. The tubular zeolite membranes are 85 cm long and 12 mm in outer diameter.g.

H. de la Cruz. Arruebo. J. [25] K. Ganguli. Template-free secondary growth synthesis of MFI type zeolite membranes. properties. Today 67 (2001) 101–107. Chaudhuri. Booske.A. 44 (1998) 1903–1913. [13] Y. A. H. Langa. and mechanistic considerations. W. Algieri. Green Chem. R. Microwave assisted synthesis—a critical technology overview. 37 (2002) 1491–1496. Technol. [27] A.666 (1988).G. E. Noack. de la Hoz. Y. Wang. Eng. Mater. progress.H. Catal. Dong. Lin. Sep. and prospects.C. Contemp. Tied. 13 (2001) 1101–1107.B. Purif. Zeolites Ordered Mesoporous Mater. [35] J. K. [30] J.H. Chem. Catal. Matsukata. Microporous Mesoporous Mater. Zeolitic membranes: synthesis. 25 (2001) 39–55. Mater.J. M.P. Method 31 (2002) 229–379. Nicolich. Dong. . Molecular sieve membranes for industrial application: problems. Controlled microwave heating in modern organic synthesis. Innovations 1 (1997) 77–84. Adv. Encyclopedia of Nanoscience and Nanotechnology. 34 (1995) 1652–1661. Technol.P. U. M. Kita. Noble. A. J. Chem. Bernal. Shattuck.A. T. Top. 6 (2004) 128–141. [52] G.. Ind. M. Noack. J. 1–19.S. Gabriel. Preparation of thin supported MFI membranes by in situ nucleation and secondary growth.H. B. Bonrath. 62 (2003) 211–220. Microporous Mesoporous Mater. Microporous inorganic membranes.S.O. Tsapatsis.X.T. Y. Halstead. 867–919. Julbe. M.778. [38] Z. J. [16] P.Y. Eng. New York. W. Beresnevicius. 26 (2003) 1207–1216. 58 (2000) 1311–1315. Huang. Schneider.E. Long. Perreux. X. [37] W. Deposition of oriented zeolite A films: in situ and secondary growth. AIChE J. Yan. Acta Chim. vol. [21] C. Sarka. P. Xomeritakis. G. A tentative rationalization of microwave effects in organic synthesis according to the reaction medium. Purif. Mater.S.C.S. Tsapatsis. 70 (1997) 2341–2356. Lautenschlager.E. Vartuli. Controlling crystal orientation in zeolite MFI thin films by direct in situ crystallization.M. microstructure. [11] J. P. Matsukata. P. Okamoto. Prospects 157 (2005) 135–160. S. Microwave-assisted reactions in organic synthesis—are there any nonthermal microwave effects? Angew. Chem. Technol. G. M. 63 (1998) 1699–1723. J. A. M. Yasumori. 27 (1998) 213–223. Rev. [22] M. 29 (2004) 29–44.G. B. E. T. J.C.C.R. [20] G.J.S. Moreno. 30 (1995) 5321–5327. Kumakiri. The control of phase and orientation in zeolite membranes by the secondary growth method. D. Y. Today 25 (1995) 209–212. D. Toussaint.C. Chem.P.J. H. R. 152 (1999) 41–59.S. 14 (2004) 716–729.D. G. 25 (2002) 221–230. [8] A. Loupy.S. pp. Wathey. Diaz-Ortiz. J. Nanostructured zeolite films. [29] F. Tsapatsis. Siliceous ZSM-5 membranes by secondary growth of b-oriented seed layers. Kuck. J. Synth. M. Microporous Mesoporous Mater. Soc. Sci. [24] P.C. M. S. Venzke.A. Vanbekkum. Chem. 8 (1996) 473–479. In situ crystallization of beta zeolite membranes and their permeation and separation properties. Chem. Soc. Microporous Mesoporous Mater. A.F. Ramsay. Kolsch. Soc.L.D. F. W. J.). 11 (1999) 975–996. Yan.C. 158 (2005) 129–136. Tompsett. Lidstrom. Y. Synthesis of oriented zeolite molecular sieve films with controlled morphologies. Mater. Cundy. Wang. Gum. Xomeritakis. Synthesis and characterization of oriented MFI membranes prepared by secondary growth. Drioli. Nair. Microporous Mesoporous Mater. 2003. Tsapatsis. 49 (2003) 237–247. Oudshoorn. [45] R. J. Gabriel. J. A.A. Chem. Gouzinis. H.S. 54 (1999) 3521–3531. Nair. Synthesis of silicalite tubular membranes by in situ crystallization. Mater. Y. Tavolaro. Rev. K. from microwave derived seeds.A. Gavalas. Chemphyschem 7 (2006) 296–319. Girnus. J. 14 (2002) 489–492. Lin. [44] X. Optimization of the preparation of binderless ZSM-5 coatings on stainless steel monoliths by in situ hydrothermal synthesis. [33] Y. 15 [34] Y. Inc. Mater.Y. Ren. Microwave preparation of zeolite-Y and Zsm-5. [43] L. J. Sep. 34 (2000) 81–91. 41 (2002) 1863–1866.L. R. US Patent 4.M. Org. Prog. 47 (2001) 127–134. W.A. Richtermendau. I. A. Jansen. Santamaria.A. Y. Res.B. Tsapatsis. Res. Zeolite membranes. H. O. Sci. On the preferred orientation and microstructural manipulation of molecular sieve films prepared by secondary growth.S.R. Microporous and dense inorganic membranes: current status and prospective. Chem. Alsyouri. [12] Y. Synthesis of AlPO4 -5 aluminumphosphate molecularsieve crystals for membrane applications by microwave-heating. Takei. Mater. Nuchter. State-of-the-art in zeolite membrane reactors. [51] M. Pohl. 11 (1999) 882–895. Ebaid. Mater. [18] I. Lovallo. Lai. H. B. Gouzinis. in: H. [49] G. Freeman. 48 (2001) 229–238. Gouzinis. A. van Bekkum. Caro. [55] A. Wang. K. Bull. Boey. Silicalite-1 zeolite composite membranes. Oriented growth of ETS-4 films using the method of secondary growth.Y. Ed. Marcel Dekker. Ed. Overney. Zhang. [42] V. B. Jansen. W. Yan. Chem. Boudreau. Thermal and non-thermal interaction of microwave radiation with materials. Shan.G. [10] M. Falconer. Chem. [15] M. Microwave synthesis of nanoporous materials. Eng. Mater. Lin.H. Microwave irradiation: more than just a method for accelerating reactions. Pan. Thermal and non-thermal microwave effects. 43 (2001) 319–327. [41] C. [17] A. Yilmaz. Yan. R. S. Kuboyama. M. pp. Li. R. Oriented zeolite MFI monolayer films on metal substrates by in situ crystallization. Tetrahedron 57 (2001) 9225–9283. [28] J. E. Int. Ondruschka. Vaidhyanathan. CoAPO-44 and ZnAPO-34 films on alumina substrates. Angew. Y.D.M. Adv. Lin. M. [23] M. A review. Conner. In situ synthesis of P-type zeolite membranes on porous alpha-alumina supports.R. Catal. Y.M. He.S. S.C.S. Caro. Tsapatsis. American Scientific Publishers.T. Zeolites 13 (1993) 162–165. Li. van Kooten. Coronas.K. Arafat. [31] L. Chem. 37 (1998) 2404–2409. Yngvesson. Adv.J.P. Growth. Yan. Kappe. Yang. Dwyer.S.Y. M. L. In situ zeolite Na-X coating on glass fibers by soft solution process. J. W. Kameshima. M. Cooper. Chem. in: K.S. Res. B. Microwave-assisted chemical reactions. J. Lin. [40] Z.F. [39] Z. Sacco.R. E. Chem. Z. [48] L. A. J.M. A. Falconer. P. Chen. Microwave enhanced reaction kinetics in ceramics.L. 18 (2006) 1107–1112. A. Chu. Sci. Y. Tetrahedron 57 (2001) 9199–9223. Catal. 34 (2005) 164–178. Ondruschka. Schafer. [9] M. In situ synthesis of B-Al-MFI-type zeolite membrane on a porous glass disc by substrate self-transformation. Diaz-Ortiz. [26] C. X. K. Davis. Kallus. Muller. [47] M.C. solutions. J.D. S. Wang. Sci. Microwave techniques in the synthesis and modification of zeolite catalysts. Sci. E.L. Warzywoda.). Sci. Li. Nalwa (Ed. Lin. 10 (1998) 2497–2504.S. Sin. Golemme. Tierney. Yoshimura. Stud. 37 (2000) 99–105. Synthesis of inorganic solids using microwaves. Ind. Microporous Mesoporous Mater.S. Funct. 245 (2004) 41–51. P. [14] H. Preparation of zeolite Zsm-5 membranes by in situ crystallization on porous alpha-Al2 O3 . Dutta (Eds. Mater. 2003. Membr. AIChE J. In situ synthesis of AlPO4 -14. Nair. M. Kikuchi. [50] M. J. Westman. C. Zeolite membranes—a short overview. S. Jpn. Membr. F.S. A. Surf. [54] A. A.S. [46] A. B. Kuhnert.N. Kikuchi. Auerbach. Chem. Mater. and permeation properties of supported zeolite (MFI) films and membranes prepared by secondary growth. [56] B.G. Calis. Julbe. Okubo. Microwaves in organic synthesis. J. Jacob. [19] C. Rao.S. M. [53] Z. van den Bleek. Chem. Diez-Barra. Collect. 4 (1997) 373–386. Eng. Ramakrishnan. de la Hoz. Chem. Noble. Tubular MFI zeolite membranes made by secondary (seeded) growth. Int. Yang / Journal of Membrane Science 316 (2008) 3–17 [7] A. Grant. Dielectric parameters relevant to microwave dielectric heating. Motuzas. M. Tuan. Syntheisis and Properties of Zeolitic Membranes. Synthesis and properties of A-type zeolite membranes by secondary growth method with vacuum seeding. Okada. Chem. J. Czech. Noble. A. 43 (2004) 6250. Microwave assisted organic synthesis—a review. [32] N. [36] K. 7 (1995) 711–714. Chia. Eng.T. Mingos. Commun. Mater. Nuchter. Synthesis and properties of MF1 zeolite membranes prepared by microwave assisted secondary growth.

Microwave-heating synthesis and gas separation performance of NaA zeolite membrane. [71] J. Liao. Chem. S. W.S. Enlarged area A-type zeolite membranes prepared by vacuum seeding method. Preparation of ceramic honeycomb filter supported zeolite membrane modules by microwave-assisted in situ crystallization. Mater. Yeung.S. Shih.H. Volle. J. S. Striebel.E. Liu. Chem. Stud. A. L. K. A. Park. Motuzas. Liu. Sanz. Dong.L.C. 15 (2004) 1120–1122. Lin. [60] C. Sci. silicalite-2 and TS-2. Chang. Hwang. Kim. K.U. Julbe. [68] D. Das. Supported zeolite membrane by vapor-phase regrowth. Synthesis of NaA zeolite membrane with high performance. Ghosh. M. TS-1. 10 (1998) 4030–4036. Sci. Kim. R. X. The effect of ageing on the microwave synthesis of zeolite NaA. Rapid synthesis of oriented silicalite-1 membranes by microwave-assisted hydrothermal treatment. J. J. Microwave fabrication of MFI zeolite crystals with a fibrous morphology and their applications. 92 (2006) 259–269. Gao.S. J.S. 23 (2005) 28–31.S. Liu. Chem. A.W.G. A. Y. J. J. Bao. Sci. D. L. Chao. W. Preparation of zeolite A membranes by microwave heating. Yang. W. Angew.D. X. [77] Z. S. Nanosized AlPO4 -5 molecular sieves and ultrathin films prepared by microwave synthesis. Y. H. J. Microporous Mater.S. Hwang. Commun. Yang. J. Korean J. H. Kameshima. Weh. S. Lee. Chin. [67] A. A. Ind.E. van der Lee. W.S. Surv. Motuzas. Koegler.L. Fast formation of NaA zeolite membrane in the microwave field. Jansen.S. Surf. Microporous Mesoporous Mater. Y. Uguina. [72] J. J.B. J.J. Baek. J. T. S. Liu. Jhung. van Bekkum. J. 68 (2004) 21–27. Heng. P. Lin. Part II. Bonhomme. Tsay.L. (1998) 1465–1466. Komarneni. Synthesis of silicalite-1 film on a quartz superface using the vapor phase transport method. Sanchez. Arafat. Kwon. Inorg. J. Microporous Mater.S. H. M. Lin.H.C. H. Beresnevicius. C. Chang. Wan. Preparation. Chem. Caro.S. Microporous Mesoporous Mater. Lett. M. Slangen. Purif. Okada.O. P. 72 (2004) 67–80. L. 90 (2006) 229–236. Cheng.C. Mo. Cheng. Y. S. Hwang. Liu. Supramolecular interactions and morphology control in microwave synthesis of nanoporous materials. Han.L. Lau. R. Hiromoto. [73] C. W.S.M. S. Girnus.Q.S. [75] X. Mater. Yang. 32 (2003) 139–149. J.H. J. Surf.E. S. Microwaveassisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane. [62] S. Chang. J. Catal. Xu. Yang.S. Mater. Julbe. Sci. Yang. Chin. characterization and properties of colloidal Silicalite-1. Z. Sci. K.H. 22 (1998) 333–341. Sci. Noack. Chem. J. Hwang.A. Y. Cheng.S. Li. Hwang. J. 25 (2001) 241–249. Shul. Marlow. Park.J.P. Chao. Membr. Sci. Asia 8 (2004) 91–110. Mater.Y. Permeation of single gases and gas mixtures through faujasite-type molecular sieve membranes. Inorg. J. 24 (2003) 1857– 1861. W. L. Chen. Motuzas. Uniformly a-oriented MFI zeolite films by secondary growth. Chao.Z. Madhusoodana. [58] J.L. 45 (2006) 1154–1158. R. Vapor phase transport synthesis of un-supported ZSM-22 catalytic membranes. J. 27 (1992) 1393–1405. L. Chen. Commun. Kim. Noble. Chen. Z. W. Res. Cundy. Microporous Mesoporous Mater.S.S. Z.E.W. R. Kolsch.B. S. Li. Park. Catal. Catal. Z. Catal. Lin. NaY zeolite membrane prepared by using pre-absorbed nanosized NaY zeolite synthesized [79] [80] [81] [82] [83] [84] [85] [86] [87] [88] [89] [90] [91] [92] [93] [94] [95] [96] [97] [98] [99] [100] [101] by microwave heating. Z.B. R. J. Z. application as medium to organize molecules for spectroscopy and nonlinear optics. Rodriguez. Well-aligned SAPO-5 membrane: preparation and characterization. 45 (2000) 1179–1181.W.T. 44 (2005) 556–560. 105 (1997) 2171–2178. W. I. Research of A type zeolite as well as zeolite membrane by microwave heating. F.S.J. Yang. Chao. Synthesis of zeolite A-type membrane with high permeation.H.S.L. Choi. J. Wan. J. Chang. Ed. Y. 11 (1997) 107–116. Plaisted. Z. Synthesis of MCM-41 using microwave heating with ethylene glycol. S. I.G. Hong. D. Sieber. 50 (2001) 33–39. K. J.W. Lin. Synthesis of zeolite NaA membranes with high permeance under microwave radiation on mesoporous-layer-modified macroporous substrates for gas separation. Jansen. Y. Bull. M. [70] J. Z. Wan. Matsukata. Liu.S. D. Microporous Mesoporous Mater. Microwave-hydrothermal synthesis of ceramic powders. Y. Chin. Madhusoodana. C. X.U. F. 41 (2006) 1481–1487. Kikuchi. Technol.S. Purif. Chem. Technol. W. Membr. Hoffmann. H. J. Yang. Chin. van Bekkum.L. Yang / Journal of Membrane Science 316 (2008) 3–17 [57] J. Chin. U.H. Losilla.Y. J. Xu.S.S.W.K. W.S. A. Zhao. Microporous Mesoporous Mater. Chen. Trudell. Synthesis of membranes of zeolites Zsm-5 and Zsm-35 by the vapor-phase method.J. Chin. Lin. Kim. Wan. Microporous Mesoporous Mater. J. Today 44 (1998) 301–308. K. 18 (2002) 528–532. Mater. A. Guizard. Chem.S.S. Noack. Some observations on the preparation and properties of colloidal silicalites. Lin. T. D. F. Xu. Chen.S. Z. 64 (2003) 33–39. P. Sci.S.S. T.C.S. Microwave synthesis of cubic mesoporous silica SBA-16. Li. 75 (2004) 173–181. Okada. [74] D. Formation mechanism of microwave synthesized LTA zeolite membranes. Coutinho. [61] Y.M. S. Chin. Das. L.P. X. Liu. Bein. Zhao. H.P. Beresnevicius. 7 (2001) 241–249. 27 (2006) 544–546. Hwang.C. Cheng. Liu. Microwave synthesis of ETS-4 and ETS-4 thin films. Huang. Huang. Kwon. J. Eng.A. Mater. Y. Dou. Jhung.X. H. M. Yang. W. J. X. Yamashita. F. Chem. L. Sci.P. Microporous Mesoporous Mater. S. X. Kim. Int. Lett. S. W. Tsapatsis.P.D. Lin. H. Eng. 18 (2003) 1306–1312. M. K. Synthesis of a zeolitic thin layer by a vapor-phase transport method: appearance of a preferential orientation of MFI zeolite. J. Kim. Julbe. 54 (2002) 27–36. Xu.G. Chang.S. Castillo. J.J.L. J. J. Yang. S. J. Ma.L. Serrano. Chin. Jhung. Univ. [65] Y. Balkus. K. 12 (2000) 195–196.W. Z.S.L. Microwaveassisted hydrothermal synthesis of zeolite films on ceramic supports. Y. Synthesis of sodalite/alpha Al2 O3 composite membranes by microwave heating. Fang. C. Membr. Liu. [76] X.S.N.S. Park. 9 (1997) 259–265. Xu.E. R. [69] S. Chiang. Ueyama. Caro. Synthesis of NaA zeolite membrane by microwave heating. Liu. 30 (1999) 321–326. Ultra-rapid production of MFI membranes by coupling microwaveassisted synthesis with either ozone or calcination treatment.C.L. K. Iii 317–318 (2006) 697–700. Wan. Park. Koo. Microwave synthesis of LTA zeolite membranes without seeding. Microporous Mesoporous Mater. Microporous Mesoporous Mater.S. J. 21 (2002) 1023–1025. Ceram. Angew. Chem.H. Kameshima.E. C. Qui. material for one-dimensional membranes. Song.S.K.S.H.16 Y. Chem. Lin. C. A. W. Tsai. Synthesis of a high-permeance NaA zeolite membrane by microwave heating. 277 (2006) 230–239.S. . Yang. Chem. Nenoff. 22 (2001) 99–100. Microporous Mesoporous Mater. H. Forrest. Z.S. Yang. K.S.W. K. 255 (2005) 201–211.L.D. 17 (2000) 241–244. J. Kornatowski. 46 (2000) 616–625. (1992) 1056–1058.N. H.L. Cheng. [78] Z. Thoma. S. L. Stud. Li. Eng. W. Synthesis regularity of NaA zeolite membrane in microwave field. Xiao. Adv. Sep.W. J. J. Liu. Liu. Catal. Synthesis of compact NaA zeolite membrane by microwave heating method. T.C. L.J. Synthesis and crystallization mechanism of zeolite TS-2 by microwave and conventional heating. Chao. H.L. 14 (2003) 874–876. Hwang. 99 (2007) 197–205. Synthesis of films of oriented silicalite-1 crystals using microwave heating. Cundy. 281 (2006) 646–657.H. Remarkable synergy between microwave heating and the addition of seed crystals in zeolite synthesis—a suggestion verified. Lett.K.K. G. H. Q. Selective formation of SAPO-5 and SAPO-34 molecular sieves with microwave irradiation and hydrothermal heating. J. Int. J. Microporous Mesoporous Mater. Bull. S. Cazevielle. E. [66] Y. AIChE J. 105 (1997) 2163–2170.S. 69 (2004) 197–208. M.H. Roy. Mintova. News from AlPO4-5: microwave synthesis. [64] Y. Catal. [59] E. X. Microporous Mesoporous Mater. Park. Lai. D. [63] C. Preparation of LTA zeolite membranes with few non-zeolite pores using microwave heating. Sep. Formation of zeolite A film on metal substrates by microwave heating. P. K. Li. Chem. Ed.

G. Layer development and growth history of polycrystalline zeolite A membranes synthesized from a clear solution. Y. [106] M. H.L. (2003) 4370–4377.L. 39 (2004) 671–673. Zah. [103] E. Krieg. Proverbio. W. Wu. C.U. J.S. Sung. Basic views on the preparation of porous ceramic membrane layers—a comparison between amorphous and crystalline layers. Shih. X. 507. Breytenbach. Yang. Microwave-driven zeolite-guest systems show athermal effects form nonequilibrium molecular dynamics.S. leading to a new method for the preparation of microporous continuous layers. Phys. Microwave assisted crystallization of zeolite A from dense gels. Smaihi. B 107 (2003) 2490–2499. Huang. Science 283 (1999) 958–960. J. Chao. E. Hwang.M. vol. Lee. Mintova.A. T. Blanco. Mater. Soc. Chen. Z. p. K.M. A. S. Bonaccorsi.K. Lee. Valtchev. Jansen. 1. Valtchev. Robson (Eds. J. Barida. Mechanism of zeolite a nanocrystal growth from colloids at room temperature. Top. J. Tompsett.C. Kulprathipanja. V. 29 (2004) 85–92. K. K. Microwave Techniques in Zeolite Synthesis.G. Tsai.H. Wang. Eur. Guo. S. Olson.C.K. U.M. H. Jansen. T.E. W. Yang / Journal of Membrane Science 316 (2008) 3–17 [102] L. 1. Li. Liu. J. J. Lett. [104] X. Chem. Blanco. 9 (1997) 1154–1157. Chem.C. Reactor engineering.J. Chem. Chem. Occelli. Sci. Aligned aluminophosphate molecular sieves crystallized on floating anodized alumina by hydrothermal microwave heating. 1992. Growth 247 (2003) 555–562. van Bekkum.S. Chung. Park. Investigation of the crystallization stages of LTA-type zeolite by complementary characterization techniques. T. S. L. [107] J. J. Nonequilibrium molecular dynamics of microwave-driven zeolite-guest systems: loading dependence of athermal effects.S. Am.Y. Kwon. Conner. Synthesis of Microporous Materials. Phys. Li. in: M. 93 (2006) 141–150.). [105] S. J.J.W. Auerbach. A. V. H. Dual-layer polyethersulfone (PES)/BTDA-TDI/MDI co-polyimide (P84) hollow fiber membranes with a submicron PES-zeolite beta mixed matrix dense- [109] [110] [111] [112] [113] [114] 17 selective layer for gas separation. Barakat. Microporous Mesoporous Mater. B 108 (2004) 13913–13920. J. Auerbach. Microwaveinduced fabrication of MFI zeolite crystal films onto various metal oxide substrates. O. Inorg. Membr. Chang. Cryst. C.H. H. Lin. McLeary. Characterization of the formation of NaA zeolite membrane under microwave radiation.C. .L. Microwave synthesis of zeolites. 277 (2006) 28– 37. W. C.C. 34 (2005) 1596–1597. J.J. [108] Y. Adv.B. Sci.E. Bein.N. J. Catal.E. Mater. S. Chem. Y. S. 124 (2002) 6250–6251.H. Yngvesson. N. Y.