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Journal of Membrane Science 316 (2008) 317

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 Signicant 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 specic 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
1. 2. 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. Specic 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 4 4 6 6 6 6 8 8 10 10 11 12 13 14 14 14

3.

4. 5. 6. 7. 8.

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).

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

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

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

Fig. 1. The accumulated number of published articles on microwave-assisted synthesis of zeolites and zeolite membranes (Scopus search).

applications of membranes, lms and coatings of zeolite and zeolite-like materials (in short called zeolite membranes in this review) have been extensively investigated. A large number of review articles [113] and several book chapters [14,15] have provided extensive coverage of this subject. In the last years, heating and driving chemical reactions by microwave energy has been an increasingly popular theme in the scientic community, and so in the elds of zeolite and zeolite membranes. The pioneer work on microwave synthesis of zeolite can be traced to 1988. In a US patent, Mobil researchers claimed the microwave synthesis of microporous zeolites, such as zeolite NaA and ZSM-5 [16]. The rst published article on microwave synthesis of zeolite appeared in 1993, in which Jansen and co-workers reported that microwave-assisted crystallization of Y-type and ZSM-5 zeolite could be nished in a much shorter synthesis time and free of undesired phase as compared with conventional heating [17]. Since then, the number of publications began to increase year by year, especially after the mid-1990s (Fig. 1). In 1995, Caro and co-workers reported the synthesis of large AlPO4 -5 single crystals by microwave heating. By embedding these AlPO4 -5 crystals in a Ni grid, a membrane with one-dimensional pore structure could be obtained [18]. After then, there has been a steadily growing interest in microwave synthesis of zeolite membranes (Fig. 1). In 1998, Cundy produced an excellent review on the microwave synthesis and modication of zeolites [19]. Recently, Tompsett et al. [20] dedicated a comprehensive review on the microwave synthesis of nanoporous materials and summarized the preparation of zeolites, mixed oxides and mesoporous molecular sieves by employing microwave energy. This present review attempts to summarize the obtained progress in microwave synthesis of zeolite membranes. Beginning with a brief introduction of microwave and microwaveassisted synthesis, the so far reported literatures on microwave synthesis of zeolite membranes will then be summarized. Furthermore, the comparison between conventional and microwave synthesis and the specic microwave effect will be discussed. Finally, an outlook on the future development of microwave synthesis of zeolite membranes will be given. Based on the results obtained in our laboratory, special attention is given to the microwave synthesis of LTA type zeolite membranes.

2. Brief introduction of microwave-assisted synthesis After several years of joint efforts of the chemists, material scientists, and microwave engineers, microwave-assisted synthesis (especially microwave assistant organic synthesis) has matured into a highly useful technique, and some review articles were published which are well worth reading [1927]. Mingos and co-workers [26] have given a thorough explanation of the underlying theory of microwave dielectric heating. Nuchter et al. [22] have given a critical technology overview and focused mostly on reaction engineering in microwave eld. In the following section, we will briey describe the basic physical principles of microwave chemistry to the membranologists who are not familiar with this subject. For more general information on the subject of microwave chemistry, the above-cited reviews are recommended. 2.1. Basic physical principles of microwaves and microwave heating Microwaves lie in the electromagnetic spectrum between infrared waves and radio waves. They have wavelengths between 0.01 and 1 m, and operate in a frequency range between 0.3 and 30 GHz. The typical bands for industrial applications are 915 15 and 2450 50 MHz. To our knowledge, all the reported microwave chemistry experiments are currently conducted at 2450 MHz (the corresponding wavelength is 12.24 cm). One reason is that near to this frequency, the microwave energy absorption by liquid water is maximal. Another probable reason is that 2450 MHz magnetrons are mostly often used in the available commercial microwave chemistry equipments. Interaction of dielectric materials with microwaves leads to what is generally described as dielectric heating due to a net polarization of the substance. There are several mechanisms which are responsible for this, including electronic, ionic, molecular (dipole), and interfacial (space-charge) polarization. For easier understanding, it can be described that in the presence of an oscillating eld, dipolar molecules try to orient themselves or be in phase with the eld. However, their motion is restricted by resisting forces (inter-particle interaction and

Table 1 LTA zeolite membranes from microwave synthesis

Substrate Synthesis strategy Synthesis Composition Copper and silicon wafer Alumina In situ 3:1:2:200, Na2 O/Al2 O3 /SiO2 /H2 O Preparation procedure 120 C for 1 min followed by 100 C for 30240 min Heated to 90 C in 1 min; held for 540 min Heated to 90 C in 1 min; held for 545 min On Cu substrates a dense lm was formed; but on stainless steel no layer-like zeolite lm was formed Four stage under microwave radiation: absorbing (015 min), nucleation, crystallizing (1525 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; high alkalinity and sodium cation concentration disfavored the formation of membranes H2 /N2 selectivity increased with increasing synthesis time. Microwave heating increased the reaction rate greatly; the thickness of the membranes could be controlled by varying the amount of the reaction mixture In situ aging time, temperature and microwave heating time have inuence on the membrane quality, in situ aging was necessary for microwave synthesis of LTA zeolite membranes without seeding The formation process of LTA membranes under microwave eld was comprehensively studied; the formation mechanism of LTA zeolite membranes was proposed Compared with conventional heating, LTA zeolite membranes with few non-zeolite pores can be synthesized by using microwave heating N.R.a Goldstar Er-4010 [68] Main results Membrane Performances Microwave oven type Reference

Seeded

3:1:2:200, Na2 O/Al2 O3 /SiO2 /H2 O

H2 /C3 H8 permselectivity was 6.23 at 25 C

Modied domestic microwave oven

[104]

-Al2 O3 modied

Seeded

Gel: 3:1:2:200, Na2 O/Al2 O3 /SiO2 /H2 O Sol: 5:1:50:1000, SiO2 /Al2 O3 /Na2 O/H2 O 36:2:1:150, Na2 O/SiO2 /Al2 O3 /H2 O

Highest H2 permeance was 2.64 106 mol s1 m2 Pa1

Modied domestic microwave oven

[75]

-Al2 O3 and -Al2 O3 Alumina

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

Seeded

Fluxed at 90 C for 425 min

N.R.

NN-K580MFS P = 100 W

[77]

Alumina

Seeded

3:2:1:150, Na2 O/SiO2 /Al2 O3 /H2 O

Fluxed at 90 C for 25 min

Alumina

In situ

1:0.85:3.0:200, Al2 O3 /SiO2 /Na2 O/H2 O

Synthesis in microwave oven at 250 W for 1520 min; dried in microwave oven at 120 W for 10 min Aging at 50 C for 7 h in air oven, and then microwave synthesis at 90 C for 25 min

H2 /N2 selectivity was 3.97; H2 permeance was 51.5 108 mol s1 m2 Pa1 N.R.

NN-K580MFS P = 100 W

[79]

N.R.

[86]

Alumina

In situ

5:1:50:1000, SiO2 /Al2 O3 /Na2 O/H2 O

H2 /N2 and H2 /C3 H8 permselectivities were 5.60 and 9.17, respectively.

HR-8801MHaier

[66]

Alumina

In situ

5:1:50:1000, SiO2 /Al2 O3 /Na2 O/H2 O

Aging at 50 C for 7 h in oven, and then microwave synthesis at 90 C for 035 min MH: aging at 50 C for 7 h in oven, and then microwave synthesis at 90 C for 25 min; CH: aging at 50 C for 7 h in oven, and then conventional synthesis at 90 C for 3h Heated to 90 C in 60 s; held for 15 min

N.R.

HR-8801MHaier

[64]

Alumina

In situ

5:1:50:1000, SiO2 /Al2 O3 /Na2 O/H2 O

Alumina

Seeded

50:1:5:1000, Na2 O/Al2 O3 /SiO2 /H2 O

Alumina

Seeded

50:1:5:1000, Na2 O/Al2 O3 /SiO2 /H2 O

Heated to 90 C in 60 s; held for 15 min

Alumina

Seeded

50:1:5:1000, Na2 O/Al2 O3 /SiO2 /H2 O

Heated to 90 C in 60 s; held for 15 min

The synthesis time was 812 times shorter than conventional heating; the permeance of the microwave synthesized zeolite membrane was increased by four times, while keeping comparable permselectivity Microwave heating greatly accelerated the zeolite membrane formation; 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; multi-stage synthesis resulted in the formation of more impurity phase

For H2 O/IPA pervaporation, microwave synthesized membranes maintained high separation factor even when water content was lower than 1% H2 /n-C4 H10 permselectivity was 11.8; H2 permeance was 213 108 mol m2 s1 Pa1

HR-8801M Haier

[65]

Modied domestic microwave oven

[84]

Permeance of O2 and N2 were 0.68 and 0.66 106 mol m2 s1 Pa1 , respectively O2 /N2 and H2 /n-C4 H10 permselectivities were 1.02 and 11.8, respectively; H2 permeance was 21 107 mol m2 s1 Pa1

Modied domestic microwave oven

[83]

Modied domestic microwave oven

[81]

a Not reported.

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

electric resistance), which restrict their motion and generate heat. Generally, materials can be classied into three categories based on their interaction with microwaves: (1) materials that reect microwaves, typied by bulk metals and alloys, e.g. copper; (2) materials that are transparent to microwaves, typied by fused quartz, several glasses, ceramics, Teon, etc.; and (3) materials that absorb microwaves which constitute the most important class of materials for microwave synthesis, e.g. aqueous solution, polar solvent, etc. Dissipation factor (often called the loss tangent, tan ), a ratio of the dielectric loss (loss factor) to the dielectric constant, is used to predict materials behavior in a microwave eld. The microwave absorption ability of a material is directly proportional to its dissipation factor. 2.2. Advantages of microwave heating Conventional heating (i.e. conduction, convection, 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. Compared with conventional heating, 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; (2) the microwave energy is introduced into the chemical reactor remotely without direct contact between the energy source and the reacting chemicals; (3) it is volumetric and instantaneous (or rapid) heating with no wall or heat diffusion effects; (4) it can realize selective heating because chemicals and the containment materials for chemical reactions do not interact equally with microwaves; (5) hot spots yielded on local boundaries by reections and refractions may result in a super-heating effect, which can be described best as local overheating and is comparable to the delayed boiling of overheated liquids under conventional conditions. 2.3. Specic microwave effect Firstly, 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, even the energy of hydrogen bond is several tens of Joules per mole). However, the numerous experimental observations on reaction rate enhancement in microwave eld, especially solid-state reactions, could not be interpreted by thermal effects of microwave solely, which leads to the concepts of non-thermal effects, also called specic microwave effect. According to the explanation of Booske et al. [28], thermal refers to interactions resulting in increased random motion of particles (e.g. atoms, molecules, ions, or electrons) where the kinetic energy statistics of such uctuations are represented by a single thermodynamic equilibrium distribution (i.e. MaxwellBoltzmann, BoseEinstein, or FermiDirac). Non-thermal effects refer to interactions resulting in nonequilibrium energy uctuation distributions or deterministic, time-averaged drift motion of matter (or both). In a previ-

ous review, Langa et al. [29] suggested the so-called specic microwave effect. Afterward, Jacob et al. [30] published an excellent review on the synthetic results to which the microwave effect has been attributed. Loupy and Perreux [31] published a tentative rationalization of non-thermal effects in organic synthesis, and Kuhnert has given a highlight to discuss the non-thermal microwave effect in organic synthesis [32]. Kappe, however, 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]. Nevertheless, this topic is still a controversial matter and open to interpretation. 3. Microwave synthesis of zeolite membranes Commonly used strategies for zeolite membrane synthesis can be classied into three categories: in situ hydrothermal synthesis [3345], secondary (seeded) growth synthesis [41,4657], and vapor phase transport synthesis [5862]. Microwave techniques combining with these strategies could create some novel synthesis routes, among which, in situ microwave synthesis [18,43,6370] and microwave assistant secondary growth [55,7185] have been reported for membrane preparation. LTA, MFI, AFI, FAU, SOD, and ETS-4 types of zeolite membranes have been successfully synthesized by microwave heating. This section is intended to be a comprehensive collection of these reports although accidental omission is inevitable. 3.1. LTA (NaA) Due to the relative simple synthesis gel/solution (containing no templates) and low crystallization temperature (usually <100 C), LTA type zeolite membranes are most extensively studied in microwave synthesis of zeolite membrane research. Table 1 summarizes the microwave synthesis conditions and main experimental results of LTA zeolite membranes. NaA zeolite membranes were microwave synthesized on alumina support by Han et al. in 1999 [86]. Microwave heating greatly accelerated the crystallization rate and reduced the synthesis time to 10 min. It was reported that the thickness of the membranes could be controlled by varying the amount of the reaction mixture. This indicates that the membrane was formed by physical deposition of crystals from the bulk onto the support. No separation data was reported for this membrane. In our group, the efforts to synthesize of NaA zeolite membranes started in the late 1990s. 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 ux, as illustrated in Fig. 2. Here, pre-seeding the support with microwave synthesized NaA zeolite was needed to overcome the nucleation-related bottleneck [87,88]. Compared with conventional heating, the synthesis time was shortened by 812 times by using microwave heating, and the permeance of the membrane was increased by 4 times, while keeping comparable permselectivity for H2 /n-C4 H10 [81,83,84]. In order to further improve the permeance and permselectivity of zeolite NaA membranes, we considered modifying the

Table 2 MFI zeolite membranes from microwave synthesis Substrate Synthesis strategy Synthesis Composition WO3 /TiO2 /Fe2 O3 /SiO2 coated glass In situ 1:0.2:22 or 100, TEOS/TPAOH/H2 O Preparation procedure Heated for 90 min at 150 C; calcinated in air at 500 C The crystal exhibited the same shape and orientation regardless of the nature of the under coatings; with the increment of the dielectric constants, the surface coverage increased Microwave heating favored a great control over the temperature prole After 10 min microwave heating and 6 h hydrothermal synthesis, membrane with 74 m thickness was obtained; increasing the microwave heating time produced denser and smaller zeolite crystals; 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. (1 0 1) oriented membrane was synthesized at 160 C, while c-orientation at 180 C MFI zeolite membranes with a (1 0 1) preferred orientation were prepared at 160 C for 2 h; three methods were used to eliminate the template: ozone treatment at 160 C for 1.5 h, calcination with a slow heating rate (0.2 C/min), and calcination with a rapid heating rate (5 C/min) N.A.a MARS-5 CEM P = 600 W [113] Main results Membrane performances Microwave oven type Reference

Silicon wafer

In situ

6.5:1:675, SiO2 /(TPA)2 O/H2 O 100:10:1800, SiO2 /TPAOH/H2 O

Cordierite honeycomb substrates and alumina disks

In situ

Rapid heating and cooling; temperature: 135200 C; duration: 340 min Heated at full power for 215 min, and then hydrothermal synthesis at 150 C for 324 h; calcinated at 600 C for 2 h

N.A.

SharpR-10R P = 50 W

[93]

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

N.A.

Domestic microwave oven; P = 800 W

[73]

Alumina

Seeded

25:3:1500:100, SiO2 /TPAOH/H2 O/EtOH

Crystallization temperature: 120180 C, duration: 30150 min Calcinated at 450 C for 4 h

Membrane with higher n/i-butane selectivity (4050) and medium permeance was synthesized at higher temperature (160 C)

ETHOS 1600, Milestone; Pmax = 400 W

[72]

Alumina

Seeded

25:3:1500:100, SiO2 /TPAOH/H2 O/EtOH

Crystallization temperature: 160 C; duration: 30150 min; Calcinated at 550 C or ozone treated at 200 C

The ideal selectivity for n/i-C4H10 lies in the range 4750 at 2050 C; the same selectivity but lower permeance was obtained for the ozone activated membrane

ETHOS 1600, Milestone; Pmax = 400 W

[71]

Not reported.

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

Fig. 2. Comparative synthesis model of zeolite membrane by microwave heating and conventional heating (redrawn from Ref. [83]).

macroporous alumina support with a thin mesoporous top-layer to prevent the penetration of the reagent into the support. The obtained result coincided with our assumption. The H2 permeance was increased by 1.53.3 times, and the permselectivity for H2 /n-C4 H10 was also increased to some extent [75]. Cheng et al. also carried out the investigation on microwave synthesis of A-type zeolite membranes [77,79,89]. Secondary growth strategy was also adopted by them, but silica-alumina gel instead of clear solution was used for zeolite crystallization. It was reported that the high alkalinity and sodium cation concentration disfavored the growth of membranes [77]. 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 [54,81,9092]. Recently, a new method called in-situ aging-microwave heating method was developed for zeolite membrane synthesis by our group. High quality NaA zeolite membranes with H2 /N2 permselectivity of 5.6 were successfully microwave synthesized without seeding by this method [64,66]. LTA zeolite membranes with excellent pervaporation performance were also prepared with high reproducibility. This method decouples two successive steps in the formation of zeolite membranes. The rst step is the rearrangement of synthesis mixture and the formation of germ nuclei on the support surface, which were obtained by in situ aging. The second step is the nucleation and crystals growth on the support, which were achieved by the consequential crystallization under fast and homogeneous microwave heating. Because articial seeding was replaced by in situ heterogeneous nucleation, a much higher nucleation rate favored by microwave heating greatly enhanced the number of nuclei on the support surface. As a result, NaA zeolite crystals could inter-grow together in a short time, and defect-free LTA zeolite membranes were thus formed. This convenient and effective

method has made the mass production of LTA zeolite membranes a reality. This aspect will be discussed in Section 7. 3.2. 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), the articles published on microwave synthesis of MFI type zeolite membranes are limited. 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]. Table 2 summarizes the microwave synthesis conditions and main experimental results of MFI type zeolite membranes. Microwave synthesis of Silicalite-1 zeolite membranes was reported by Koegler et al. Films containing oriented 100 nm Silicalite-1 crystals have been in situ synthesized on a silicon wafer using rapid heating and cooling [93]. Combining microwave heating with secondary growth strategy, Motuzas et al. synthesized Silicalite-1 zeolite membranes on alumina supports with (1 0 1) and (0 0 1) preferred orientation [72]. The morphology, thickness, homogeneity, crystal preferential orientation (CPO) and single gas permeation properties of the Silicalite-1 membranes have been studied in relation to the synthesis parameters. The ideal selectivity for n/i-C4 H10 was in the range 4050. Recently, 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]. 3.3. AFI (AlPO4 -5 and SAPO-5) In 1995, Caro et al. [18] reported the microwave synthesis of large AlPO4 -5 single crystals. These crystals could be

Table 3 AFI zeolite membranes from microwave synthesis

Substrate Synthesis strategy Seeded Synthesis Composition Ni grid 1:1.3:1.6:1.3:425:6, Al2 O3 /P2 O5 /TEA/HF/H2 O/iC3 H7 OH Preparation procedure Heated to 180 C for 60 s Microwave greatly accelerated the formation of AlPO4 -5 zeolite without any impurity; oriented membrane showed excellent selectivity based on the molecular size c-Oriented growth of AlPO4 -5 was obtained by microwave heating; 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 Morphology, orientation, and size of the AlPO4 -5 crystals could be controlled by experimental conditions; microwave heating led to homogenous lm growth and microporosity Separation factor: n-butane/triisopropyl-benzene = 1220; n-heptane/triethylbeneze = 105; n-eptane/mesitylene = 1.7; n-heptane/toluene = 0.8 N.A.a MLS1200; Pmax = 1200 W [18] Main results Membrane performances Microwave oven type Reference

Anodized alumina

Seeded

1:1.3:2.4:1.3:425, Al2 O3 /P2 O3 /TEA/HF/H2 O

Heated at 180 C; ultrasonicated, washed and dried at 90 C for 1 h

MDS 2000; CEM

[114]

Anodic Alumina

Seeded

1:1.3:0.10.45:2.4:1.3:425, Al2 O3 /P2 O3 /TEOS/TEA/HF/H2O

Gold coated quartz crystal microbalances (QCM)

a Not reported.

Seeded

1:1.281.32:0.71.0:50900, Al2 O3 /P2 O5 /(TEA)2 O/H2 O

Heated at 185 C for 2.54.5 min; ultrasonicated, washed and dried at 90 C for 1h Reaction temperature: 90150 C; duration: 110 min; microwave power: 3001000 W; calcinated in oxygen at 350 C over night

N.A.

MDS 2000; CEM Qwave 3000; Questron

[85]

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

N.A.

[69]

Table 4 SOD, FAU and ETS-4 zeolite membranes from microwave synthesis
Membrane type SOD Synthesis strategy In situ Synthesis Composition 50:1:5:1000, Na2 O/Al2 O3 /SiO2 /H2 O 1:5:50:1000 or 1:0.85:3:200 or 1:3.5:50:1000 or Al2 O3 /SiO2 /Na2 O/H2 O Preparation procedure Heated to 90 C in 60 s and held for 1545 min; multi-stage synthesis Reaction temperature: 160200 C; duration: 15180 min Microwave heating not only promoted the formation of SOD membrane but also inhibited the formation of impurity The pre-seeding/secondary growth method, involving seeds prepared by microwave heating, was used to synthesize larger area and homogeneous SOD membranes with good reproducibility Dense inter-grown FAU layers with Si/Al ratios of 1.31.8 and layer thicknesses in the range of 0.86 m were obtained; microwave heating resulted in a higher Si/Al ratios of the membrane Microwave heating greatly accelerated the reaction rate; meanwhile it could curb the formation of impurity phase H2 /n-C4 H10 permselectivity >1000; permeance of H2 was 1.14 107 mol m2 s1 Pa1 N2 and He permeances were typically in the range 0.52 108 mol m2 s1 Pa1 ; highest selectivity was 6.2 Modied domestic microwave oven ETHOS 1600 Milestone P = 250 W [76] Main results Membrane performances Microwave oven type Reference

SOD

In situ and seeded

[67]

FAU

Seeded

1:10:14:840, Al2 O3 /SiO2 /Na2 O/H2 O

Reacted at 120 C for 2 h; repeated twice

ETS-4

Seeded

16:1:11.33:761.3:8.5, NaOH/TiO2 /SiO2 /H2 O/H2 O2 (pH 12.1)

Pulse laser deposition was used for surface seeding; reacted at 235 C for 2060 min

Permeance order: H2 > CH4 > N2 > O2 > CO2 > nC4 H10 > SF6 at 23 C, N2 /CO2 permselectivity was 8.4; CH4 /CO2 permselectivity was 3.5 N.A.a

MLS 1200 MLS GmbH Leutkirch

[80]

MARSX-press CEM

[74]

a Not reported.

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Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

formed in as little time as 60 s, and were found to be ideal for one-dimensional molecular sieving. Mintova et al. [69] used microwave heating to prepare thin lms of AlPO4 -5 on gold coated quartz crystal microbalances (QCMs). The temperature, microwave heating time, power, and aging time affected the thickness and orientation of the zeolite crystals. Films prepared by conventional heating showed no crystal orientation. Tsai et al. [85] prepared well-aligned SAPO-5 membrane using microwave heating on an anodized aluminum substrate. Various sets of samples with different silicon contents in reactant gels and different reaction times in secondary microwave hydrothermal heating were studied. 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. Table 3 summarizes the microwave synthesis conditions and main experimental results of AFI type zeolite membranes. 3.4. Others (SOD, FAU and ETS-4) Some other types of zeolite membranes have also been synthesized by adopting microwave heating, as summarized in Table 4. Julbe et al. [67] have evaluated the potential of microwave heating for synthesizing sodalite membranes on tubular supports. 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. In order to overcome this problem, the authors developed another indirect strategy, the pre-seeding/secondary growth method, which allowed the synthesis of larger and homogeneous samples with a good reproducibility. 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]. Only 45 min was needed by this method, more than eight times faster than by the conventional hydrothermal synthesis method. A pure hydroxy-sodalite zeolite membrane was easily synthesized by microwave heating method, while a zeolite membrane, which consisted of NaX zeolite, NaA zeolite and hydroxy-sodalite zeolite, was usually synthesized by conventional heating method. The pure hydroxy-sodalite zeolite membrane synthesized by microwave heating method was found to be well inter-grown. The gas permeation results showed that the H2 /N2 permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. Weh et al. 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]. Two different kinds of heating were used in the secondary growth step, either conventional heating or microwave heating. Engelhard titanosilicate (ETS-4) has octahedral coordination in addition to tetrahedral coordination, and recently it was successfully synthesized as a membrane form by pulsed laser deposition (for seeding) and microwave treatment (for secondary growth) [74]. Microwave irradiation shortened the synthesis time considerably as compared to conventional heating, which

resulted in the rapid synthesis of ETS-4 in less than 1 h compared to 3648 h for the traditional synthesis. 4. Comparison between microwave heating and conventional heating synthesis In the above section, it has been shown that compared with conventional heating, microwave heating can remarkably reduce synthesis time. This is one of the most frequently mentioned advantages of microwave synthesis. In this section, we will mainly discuss the differences in membrane characteristic and performance of the membranes synthesized by microwave heating and conventional heating. In the synthesis of porous materials, it has been reported that the microwave synthesis method could provide an efcient way to control particle size distribution [9497], phase selectivity [98], and macroscopic morphology [96,99102]. In the case of zeolite membranes, microwave synthesis also leads to different membrane characteristics from those synthesized by conventional heating [6466,8082,84]. Our recent studies found that microwave assistant hydrothermal synthesis can be an efcient tool for the morphology control of LTA type zeolite membranes. As shown in Fig. 3, a LTA zeolite membrane synthesized by conventional heating is composed of well-shaped cubic LTA crystals, while the membrane synthesized under pulsing microwave irradiation consists of sphere grains without well-developed crystal faces. Under continuous microwave irradiation, however, bundles of layered crystals form the tightly packed membrane. Besides this morphological difference, microwave synthesis can also lead to a compositional difference of the synthesized zeolite membranes. For examples, Weh et al. [80] reported that when using microwave heating instead of conventional heating, the as-synthesized FAU type zeolite membrane had a slightly increased Si/Al ratio (from 1.4 to 1.8). In our study, we have also found that microwave heating is favorable for the synthesis of the high silica analogue of FAU type zeolite membranes, i.e. Y-type zeolite membranes. In our researches on microwave synthesis of LTA type zeolite membranes, it was interesting to nd that the as-synthesized NaA zeolite membrane had a Si/Al ratio of 1.43 as determined by XPS characterization, which is higher than the common value of NaA zeolite [6466]. 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. Although NaA zeolite membranes synthesized by microwave heating in short time usually had high permeance, the permselectivity of the membranes was not very high (permselectivity for H2 /N2 was just around the Kundsen diffusion ratio), as shown in Table 1. 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 5.60) while maintained the membrane permeance high. We attributed this to the distinctive morphology of microwave synthesized LTA zeolite membranes (sphere grains with undened crystal facets) from that of conventional heating synthesized

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

11

Fig. 3. SEM images of conventional heating and microwave (both pulsed and continuous) heating synthesized NaA zeolite membranes.

one (well-shaped cubic crystals) (see Fig. 3). As pointed out by Mcleary and Jansen, the ever-occurring triangularly shaped gap between growing crystals on the support would lead to the systematic imperfections of the synthesized membranes, and the formation of sphere grains with undened crystal facets was necessary to achieve a pinhole-free continuous zeolite layer [103]. The compactness difference between microwave heating and conventional heating synthesized NaA zeolite membranes was also conrmed by pervaporation separation test [65]. As for the membrane synthesized by microwave heating (Fig. 4), as the water concentration in feed (WF ) decreased from 9.6 to 0.2 wt.%, the water concentration in permeate (WP ) varied from 100.0 to 90.0 wt.%, with the permeation ux decreasing approximately linearly from 0.86 to 0.08 kg m2 h1 . However, for the membrane synthesized by conventional heating, when WF broke through 2.0 wt.%, WP decreased rapidly. When WF was 1.0 wt.%, WP was only 18.0 wt.%, and at the same point, the permeate ux abnormally increased dramatically. This indicated that the membrane synthesized by conventional heating might have quite a few non-zeolitic pores (in nano-size). When WF was low, the adsorbed water were not enough to block the defects to inhibit isopropanol permeation, thus much isopropanol began to pass through the pores, which leaded to a decrease in WP and increase in permeate ux. 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. In our studies on FAU type zeolite membranes, we also found that microwave heating could be an effective tool to improve membrane compactness, e.g. the pervaporation selectivity of Ytype zeolite membranes for ethanol/water were increased from 60 to more than 300 by using microwave heating. 5. Formation mechanism of zeolite membranes under microwave irradiation Up to now, the study on microwave synthesis of zeolite membranes is still at the initial stage, and the optimization of zeolite
Fig. 4. Comparison of pervaporation performances between NaA zeolite membranes synthesized by microwave heating and conventional heating. Wp: the water concentration in permeate.

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Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

Fig. 5. Schematic illustration of the proposed formation mechanism of NaA type zeolite membrane synthesized by an in-situ aging-microwave heating method (after Ref. [63]).

membrane synthesis is still a trial-and-error procedure, which is low effective and difcult to be generalized. Therefore, a fundamental understanding of the formation mechanisms of zeolite membranes is of great signicance, but the relevant reports on the formation mechanism rather rare. 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) [81,104]. Recently, we adopted gravimetric analysis, XRD, SEM, XPS, 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, and the formation mechanism of LTA zeolite membranes was proposed [64], as illustrated in Fig. 5. With this mechanism, a gel layer is rst formed on the support after in situ aging, which contains plenty of prenuclei. During the following microwave assistant crystallization, these pre-nuclei rapidly and simultaneously develop into crystal nuclei, and then crystal growth by propagation through the amorphous primary particles (with size of ca. 50 nm) goes on, and nally, the amorphous particles transform into LTA crystal particles with the same size. This propagation growth process is accompanied by the agglomeration and densication of the primary particles. In this way, compact LTA zeolite membranes

consisting of spherical grains with undened crystal facets are obtained. Based on the above results and referred to the reported formation mechanism of LTA zeolite [105,106], it is believed that the essential mechanism of zeolite formation is similar what ever in powder form or membrane form. This observation is in accordance with Zah et al.s latest report on the formation mechanism of conventional heating synthesized LTA zeolite membranes [107]. Therefore, it can be concluded that the function of microwave irradiation during zeolite membrane formation is mainly derived from its thermal effect. However, it is still suspected that there will be some specic microwave effects, and this will be discussed in the following section. 6. Thermal and non-thermal effects In order to distinguish between thethermal effect and the non-thermal effect in the synthesis of the NaA zeolite membranes by microwave heating, in our previous study [81], the following experiment was designed. A seeded support was placed in the synthesis mixture and heated up quickly to 90 C in a microwave oven, and then the synthesis system was transferred to a conventional oven, which was preheated to 90 C.

Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

13

Fig. 6. Pilot scale vapor permeation dewatering installation with 0.8 m2 membrane area.

After 15 min of synthesis, the as-synthesized membrane was characterized by XRD. It was observed that there is no signicant difference in the intensity of the diffraction patterns of NaA zeolite between the as-synthesized membrane and the seeded support. 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. Thus, we concluded that the fast formation of NaA zeolite membranes by microwave was mainly promoted by the non-thermal effect [81]. Recently, 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]. Different from what we have concluded before [80], it was found that the linear growth rate of NaA zeolite under microwave eld was at the same level as under conventional heating conditions. This indicates that microwave does not enhance the crystallization kinetics of NaA zeolite, and the acceleration effect of microwave synthesis is mainly a result of fast and simultaneous nucleation. On the other hand, we have investigated the preparation of NaA zeolite membranes with different pulse lengths of microwave irradiation. 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. This indicates that the existence of non-thermal effects can not be completely ruled out. Based on the comparison of the conventional heating synthesis and microwave heating synthesis, combined with some qualitative theoretical analysis, the thermal and non-thermal effects of microwaves during in-situ aging-microwave heating synthesis are speculated as bellow: Thermal effects: (1) selective heating, i.e. microwaves selectively couple with the gel layer because the gel phase has a

higher dissipation factor (tan ); (2) volumetric heating, i.e. the gel layer is heated quickly and entirely and homogeneously, which results in a simultaneous nucleation and synchronous propagation of crystallization. Non-thermal effects: (1) electric double layer structures of the primary particles are destroyed through MaxwellWagner polarization mechanism, which enhances the agglomeration of these particles; (2) the H-bonds are destroyed under microwave irradiation, which increases the reaction rate in the gel phase. This coincides with the active water concept proposed by Jansen et al. [109]; (3) the Si O (Al O ) bonds on the surface of the primary particles are selectively activated by microwaves, which hastens the densication between agglomerated particles. This proposal is referred to the reports of Hwang et al. [100] and Blanco et al. [110,111]. The acceleration effect of microwave synthesis is mainly due to its thermal effects, whereas, the extraordinary morphology of the microwave synthesized LTA zeolite membranes is mainly a result of the non-thermal effects of microwave synthesis. 7. 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, temperature proles and control within the synthesis autoclave are necessary. Microwave heating is a promising solution to solve this problem. In microwave processing, energy is supplied by an electromagnetic eld directly to the material. This results in a rapid heating throughout the material with reduced thermal gradients. Volumetric heating can also reduce processing times, and thus the density gradients caused by sedimentation under the gravity eld will not be signicant any longer. In addition, the uniformity of the microwave eld (multi-mode applicators) can be

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Y. Li, W. Yang / Journal of Membrane Science 316 (2008) 317

improved by increasing the size of the oven cavity. In terms of industrial production, fast and energy-saving microwave heating can lower the fabrication cost and make the continuous production possible. Therefore, microwave synthesis of zeolite membranes is especially promising for industrial production. Combining hydrothermal synthesis and microwave heating technique, scaling-up of NaA zeolite membrane has been achieved in our group. A pilot scale vapor permeation dewatering installation based on NaA zeolite membranes has been set up recently, as shown in Fig. 6. This installation produces 225 L/D fuel ethanol containing less than 0.3 wt.% water from the bio-ethanol with 10 wt.% water. The vapor permeation process is operated at 110 C and 0.2 MPa. The separation unit consists of four modules with a total permeation area of about 0.8 m2 ; each module is made up of 7 NaA zeolite membrane tubes. The tubular zeolite membranes are 85 cm long and 12 mm in outer diameter. Based on the data obtained on this installation, it is calculated that the energy consumption of zeolite membrane based vapor permeation dewatering process is much smaller than that of azeotropic distillation, pressure swing adsorption and polymeric membranes. Due to the very high water selectivity of microwave synthesized NaA zeolite membranes, ethanol recovery of >99.8% was obtained. Long term stability test (>1500 h, still carrying on now) showed that microwave synthesized NaA zeolite membranes provide very good stability in vapor permeation. Now, a 5000 tonnes per year organic dewatering plant and a reaction-separation integrated unit based on NaA zeolite membrane (microwave synthesized) are in construction. 8. Concluding remarks and future perspective Microwave synthesis is a promising method for the fast synthesis of zeolite membranes. LTA, MFI, AFI, SOD, FAU and ETS-4 types of zeolite membranes have been reported to be successfully synthesized under the irradiation of microwaves. Besides remarkably accelerating the zeolite membrane formation, inhibiting the formation of impurity is another main advantage of microwave synthesis, which has been observed by many researches in numerous cases. Due to the unique features of microwave heating, e.g. volumetric and instantaneous (or rapid) heating, specic and selective heating, reaction acceleration effect, and the so-called specic microwave effect (although there is still controversy), microwave synthesis is especially suitable for mass production of large-area zeolite membranes. This has already been realized in the case of NaA zeolite membranes in our group, which can be seen as a milestone in the development of microwave synthesis of zeolite membranes. Scaling-up microwave synthesis of FAU type zeolite membranes is ongoing in our group now. Bundled synthesis of hollow ber supported zeolite membranes, taking the advantage of microwave volumetric heating, are planned to be carried out in the near future. Comparison between microwave heating and conventional heating has been performed preliminarily, especially in the case of LTA type zeolite membranes. It was found that besides the often mentioned microwave accelerating effect, microwave syn-

thesis could also result in different membrane morphology, orientation, composition, and thus in different permeation characteristics as compared with conventional heating synthesized ones. Attempts have been made to understand the formation mechanism of zeolite membranes under microwave irradiation. As for LTA zeolite membranes, it was found that the essential mechanism of zeolite formation is similar, whether under microwave or conventional heating conditions. Therefore, it was concluded that the function of microwave irradiation during zeolite membrane formation is mainly derived from its thermal effect. However, it is still suspected that there will be some specic microwave effects, such as active water, selective activation, etc. Signicant progress has been achieved in the past several years on microwave synthesis of zeolite membranes. Nevertheless, it is still in the early stages of development, and further research is required to expand the research area, to improve the membrane performance, to increase the synthesis reproducibility, and to scale-up membrane production. This needs the interdisciplinary cooperation among material science, physical chemistry and microwave engineering. First of all, the reactor engineering must be considered in order to understand and control microwave synthesis, as pointed by Conner et al. [112]. In addition, in order to understand the formation mechanism and to provide generalized guidance for the microwave synthesis of zeolite membranes, in situ characterization of the changes in chemistry and physics (energy transfer) are required, such as neutron and X-ray scattering, and vibrational spectroscopy (refer to Tompsett et al.s review [20]). Comprehensive characterization of the chemical and physical changes during microwave synthesis and in-depth theoretical analysis, e.g. non-equilibrium thermodynamics and molecular dynamics, are the basis for understanding the real function of microwave irradiation in synthesis, including thermal and non-thermal effects. Acknowledgements This work was supported by the Ministry of Science and Technology of China (Grant No. 2003CB615802), BP and Youth Science Fund of DICP (No. S200609). References
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