5.

4 Zeolites

Zeolites are the naturally occurring crystalline three dimensional aluminosilicate microporous system which is interlinked
by oxygen atom and possess specific molecular pores, channels and cavities [76–82] (Table 1, entries 49–61). Hence, they are
widely used in/as an ion-exchangers, solid-acid catalysts and material adsorbents in various sectors like petroleum industry,
oil-refining plants, water purification, effluent treatment and waste water treatment plants [76–78]. Zeolites can be designed with
appropriate variation according to their func- tional applications and textural properties [79–82]. Nandiwale and Bokade used
various zeolites based catalyst such as micro/meso-HZ-5 zeolite (Table 1, entries 49–52) [76], modified H-ZSM-5 (Table 1, en-
tries 54) [78], hierarchical H-ZSM-5catalyst [81] for esterification of levulinic acid into various renewable alkyl levulinates (Table
1, entry 60). All these used catalysts offer excellent yield and recyclability for levulinate ester synthesis. Patil, et al., [77] carried
out synthesis of ethyl levulinate by applying bimodal micro- mesoporous H/BEA-zeolite de- rivative (Table 1, entry 53).
Nandiwale et al., [80] as well as Maheria and Dalai [79] performed synthesis of ethyl levulinate and butyl levu- linate which was
catalyzed through active and recyclable desilicated and acidic zeolites respectively (Table 1, entries 55–59). Nandiwale et al.,
[82] performed optimization via response surface methodology for modified H-ZSM-5 catalyzed synthesis of octyl levulinate
(Table 1, entry 61).
The zeolites H-BEA offers better yield due to presence of tri-direc- tional 12-member-ring whereas, H-MOR, H-SM-5 are
mono-directional and bi-directional zeolites respectively which possess the diffusion limitations for the reactant molecules. The
excellent synthesis of levu- linate compounds can be achieved by modified desilicated H-ZSM-5 as compared to original H-ZSM-
5 due to the increase of surface area. Desilication process involves selective extraction of silicon which causes increment of
effective surface area, generation of meso-porosity and improvement of mass transfer at active catalytic sites. [64,79,80]. Effect of
various structural features such as different kinds of zeolites geometry (tri-directional 12-member-ring, mono-directional 12-
member-ring and bi-directional 10-member-ring) are useful to control the catalytic process, zeolites acidity, surface area, channel
size, pore size, Si/Al ratio and crystalanity according to reaction system.
In conclusion, zeolites are highly selective in function, due to pre- sence of the uniform molecular pore/channels/cavities which
allows entry of selective molecules depending on the size of pore/channels/ cavities [77–81]. However, a major challenge
associated with the zeolite is the thermal stability and tedious designing according to their proper applications which may
hamper the acidic catalytic properties [47–49]. Internal mass transfer diffusion limitations should be elimi- nated for effective
catalysis. During modification, uniform dispersion of the metals or heteropolyacid and size of pores/cavities/channels is task of
skill-full hand.