Example crystallization enhanced selectivity

EXAMPLE 11-2 Enhanced Selectivity of a Consecutive-Competitive Reaction by Crystallization of the Desired Product During the Reaction... 

Zeolite crystal size can be a critical performance parameter in case of reactions with intracrystalline diffusion limitations. Minimizing diffusion limitations is possible through use of nano-zeolites. However, it should be noted that, due to the high ratio of external to internal surface area nano-zeolites may enhance reactions that are catalyzed in the pore mouths relative to reactions for which the transition states are within the zeolite channels. A 1.0 (xm spherical zeolite crystal has an external surface area of approximately 3 m /g, no more than about 1% of the BET surface area typically measured for zeolites. However, if the crystal diameter were to be reduced to 0.1 (xm, then the external surface area becomes closer to about 10% of the BET surface area [41]. For example, the increased 1,2-DMCP 1,3-DMCP ratio observed with decreased crystallite size over bifunctional SAPO-11 catalyst during methylcyclohexane ring contraction was attributed to the increased role of the external surface in promoting non-shape selective reactions [65]. 

Such equilibria are driven by thermodynamics and therefore a selective synthetic route towards one of these species and isolation of such heteroleptic zincates in pure form is often very difficult or impossible. Only if one of the species has a sufficiently enhanced thermodynamic stability compared to the others in the equilibrium is its isolation as a pure compound possible. This is often the case when the various groups bound to zinc have a sufficiently different electronegativity, for example when one of the groups is bound to zinc via a heteroatom, or when the steric requirements of the groups bound to zinc are rather different. Sometimes it is possible to isolate one of the species present in the Schlenk equilibrium as a solid material, for example when one of the species preferentially crystallizes from solution. 

Cymene or isopropyltoluene is produced via alkylation of toluene with propylene. Cymene is an important intermediate in the production of cresol, and it is also used as an industrial solvent. Again, for both environmental and economic reasons, the use of zeolitic materials for this conversion has been studied. For example, Flockhart et al. have used zeolite Y to effect this reaction (7). They observed that the state of the zeolite, including its degree of ion-exchange and the temperature at which it was calcined, strongly affected the distribution of cymene isomers obtained. In order to enhance the selectivity to para-cymene, the direct precursor to para-cresol, various studies have focused on the use of surface modified zeolites, for example, ZSM-5 materials, including those produced by chemical vapor deposition (CVD) of silicate esters. These species serve to reduce surface acidity and change limit diffusion within the crystal. 

The nature of the crystal, the type of anticathode, the excitation current and voltage and the choice of collimator (fine or coarse) are important parameters in optimising the search for trace elements. For example, a fine collimator should be preferred if the continuous background close to the line is high (case of an As Ka line). On the other hand, a coarse collimator would be selected if background noise is low in order to enhance the sensitivity of the measurement (case of light elements Na, Al, Si, Cl, S, etc.). 

Examples in this chapter include sterile crystallization of a labile compound, yield enhancement by crystallization, yield and selectivity enhancement, removal of low-level impurities via crystallization from the melt, crystal formation in vials in a freeze drier, and non-equilibrium resolution of stereoisomers by crystallization. These examples represent unique crystallization processes designed for specific purposes. One lesson to be learned from examination of these nonmainstream applications is that understanding of principles can lead to inventive solutions to problems. For instance, in Examples 11-2 and 11-3, the solubility difference between starting material and desired product is used to optimize the reaction yield/selectivity by crystallizing the product and protecting it from overreaction. 

Needle-like and plate-like crystals create additional process complications. For example, these crystals generally have higher filtration resistance and poorer solid flow characteristics for formulation than cube-1 ike crystals. Therefore, it is highly desirable to grow thicker crystals. To grow thick crystals, experimentally, we should try to find the best solvent which favors the formation of such crystals. Meanwhile, solvates and hydrates may form in different solvent environments. Chemical forms, such as salt, free base, and free acid, can also be evaluated. Also, control of release of supersaturation and selection of crystallization conditions to enhance crystal growth over nucleation, which are addressed in the later chapters, would be very helpful. 

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