Thesis submitted in fulfilment of the requirements for the degree Doctor technologiae (engineering: chemical) In the faculty of engineering at the cape peninsula university of technology / Since the first uses of hollow-fiber membrane bioreactors (MBR’s) to immobilize whole cells were reported in the early 1970’s, this technology has been used in as wide ranging applications as enzyme production to bone tissue engineering. The potential of these devices in industrial applications is often diminished by the large diffusional resistances of the membranes. Currently, there are no analytical studies on the performance of the MBR which account for both convective and diffusive transport. The purpose of this study was to quantify the efficiency of a biocatalytic membrane reactor used for the production of enzymes. This was done by developing exact solutions of the concentration and velocity profiles in the different regions of the membrane bioreactor (MBR). The emphasis of this study was on the influence of radial convective flows, which have generally been neglected in previous analytical studies. The efficiency of the MBR was measured by means of the effectiveness factor. An analytical model for substrate concentration profiles in the lumen of the MBR was developed. The model was based on the solution of the Navier-Stokes equations and Darcy’s law for velocity profiles, and the convective-diffusion equation for the solute concentration profiles. The model allowed for the evaluation of the influence of both hydrodynamic and mass transfer operating parameters on the performance of the MBR. These parameters include the fraction retentate, the transmembrane pressure, the membrane hydraulic permeability, the Reynolds number, the axial and radial Peclet numbers, and the dimensions of the MBR. The significant findings on the hydrodynamic studies were on the influence of the fraction retentate. In the dead-end mode it was found that there was increased radial convective flow, and hence more solute contact with the enzymes/biofilm immobilised on the surface of the membrane. The improved solute-biofilm contact however was only limited to the entrance half of the MBR. In the closed shell mode there was uniform distribution of solute, however, radial convective flows were significantly reduced. The developed model therefore allowed for the evaluation of an optimum fraction retentate value, where both the distribution of solutes and radial convective flows could be maximised.

De par leur morphologie, les cristaux creux de zéolithe permettent d’étudier les phénomènes de limitations diffusionnelles en catalyse et également d’encapsuler des particules métalliques ; les nano-réacteurs ainsi obtenus ont montré des activités catalytiques originales. Leur synthèse, qui nécessite des caractéristiques structurales particulières, a longtemps été limitée aux zéolithes de structure MFI. Le but de cette thèse était d’étudier différentes voies de synthèse pour préparer des cristaux creux de zéolithe Beta, une des zéolithes les plus utilisées dans l’industrie. Deux voies ont été suivies : l’utilisation d’un zincosilicate de même structure que la zéolithe Beta comme gabarit sacrificiel et une méthode plus classique de désilication sélective. L’encapsulation de nanoparticules de platine dans les cristaux obtenus selon la première voie a été confirmée par l’hydrogénation d’aromatiques substitués. L’’influence de la morphologie sur la diffusion de différentes molécules a été étudiée par ZLC : le temps caractéristique de diffusion a été réduit de 30 à 83 % par rapport à des cristaux conventionnels. Malgré cela, la présence d’une cavité dans les cristaux de zéolithe Beta n’a pas d’effets sur l’activité catalytique dans les réactions d’hydro-isomérisation du nC16 et du craquage du cyclohexane. La thèse discute de la présence/absence de limitations diffusionnelles / Hollow zeolite single crystals have received particular interest in catalysis. The presence of a large cavity in these model zeolites enables the study of diffusional limitation in Catalysis. The cavity also enables the encapsulation of metal nanoparticles. However, their synthesis requires specific structural characteristics and it has been limited for long to zeolites with the MFI structure. The objective of this PhD work was to investigate the synthesis of hollow Beta zeolites (*BEA framework type) and study the impact of the hollow morphology on molecular diffusion and catalysis. Two different strategies have been envisaged: a dissolution/recrystallization approach using CIT-6, a zincosilicate with the same *BEA topology and a selective desilication route. Pt nanoparticles encapsulated in hollow crystals obtained from CIT-6 showed remarkable size-selectivity in the hydrogenation of aromatics. The effect of the hollow morphology in molecular diffusion was studied using the ZLC technique; the characteristic diffusion time of the hollow morphology was reduced by 30-83% compared to the corresponding bulk zeolite. Despite that, the hollow structure had no influence on the catalytic activities for the hydroisomerization of n-C16 and for the cracking of cyclohexane. The presence/absence of diffusional limitation is discussed