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Figure 1b shows a MFI membrane obtained by seeding of ball milled silicalite used for the functionalization of an inert alumina microfiltration layer (denoted as III in Figure 1b) located on a macroporous Al2O3 support. Thus, the resulting MFI seed layer (denoted as II in Figure 1b) acts both as heterogeneous nucleation site and as flexible distance holder between support and MFI membrane, suppressing defect formations during thermal template removal. Onto the MFI seed layer the MFI membrane layer (denoted as I in Figure 1b) was formed by hydrothermal synthesis [67]. Of course, both archetypes provide different properties. The thin membrane from Figure 1a offers high flux whereas the membrane in Figure 1b possesses high pressure stability. Parasitic twin crystals were identified as defect-forming during the thermal removal of the structure directing agent (SDA) and should be prevented. By using a low SDA/Si reactant ratio (≤0.05) it was found, the formation of twin crystals can be reduced [40]. Alternatively, SDA-free zeolite syntheses are available [39,41], and a template-free secondary growth synthesis of MFI type zeolite membranes [73] is known for nearly 15 years. On the search of the most efficient synthesis technique, several more methods were reported. A secondary growth method with vacuum seeding for the preparation of A-type zeolite membranes [74] and diverse techniques for crystal orientation in zeolite membranes [75–82] were proposed. A vapor-phase transport (VPT) method was first reported by Xu et al. as an alternative approach to the hydrothermal synthesis for the preparation of ZSM-5 zeolite [83]. The VPT method was extensively studied by Matsukata et al. for the synthesis of defect-free zeolite-alumina composite membranes [84], MFI-type zeolitic membrane [85] as well as preferentially oriented MFI layers [86], compact ferrierite (FER)-alumina composite layer [87,88], where a dry aluminosilicate gel layer was deposited on the support and then further crystallized under vapors of amines and water. Besides, the achieved progress in microwave assisted syntheses of zeolite membrane has been outlined by Li et al. [89]. Gascon and coworkers debated on the limitations of the existing preparation techniques and evaluated future perspectives of zeolite and zeolite-type materials for membrane production [19]. For further reading on the progress in the seeding and secondary growth techniques used for the preparation of zeolite membranes two recent reviews are recommended [42,48]. 2.2. Permeation in Zeolite Membranes According to Weisz, classical catalytic reactors should work in a certain “window of reality” in order to run efficiently. Consequently, the optimal space time yield of a conventional membrane reactor should be centered around STY = 10−6–10−5 mol·cm−3·s−1 [90]. Weisz explained this window with time limitations at the lower border and issues on mass 7PDF Image | Zeolite Catalysis
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