Supercritical mass transfer kinetics

Micro-encapsulation, as obtained by continuous SAS techniques, is a physical process, guided both from thermodynamics and kinetics. The entire process involved is not clear. Mass-transfer kinetics and thermodynamic equilibria related to polymer-particle precipitation from a solution expanded by supercritical CO2 are currently being investigated [9,10], Many empirical observations are now available, suggesting that for a given polymeric solution, both pressure and temperature play an important role in determining the precipitated particles morphology. 

Eor economic reasons it is best to do the extraction as fast as possible by increasing the flow rate of the supercritical gas. This is, however, limited by the pressure drop from inlet to outlet of the extractor which should not exceed 10 bar in order to avoid compaction and chaimelling. The maximal flow depends on the geometry of the extractor and on the nature and particle size of the material. Other limiting factors especially towards the end of the process are diffusion and mass transfer kinetics which require time rather than large amounts of solvent. 

In summary, the kno vledge of both the phase equilibrium data and the mass transfer kinetics is essential for the speciflcation of supercritical processes. As an example. Figure 8.2 sho vs the vell-kno vn data for solubility of seed oil in CO2 and the corresponding kinetic profile of oil extraction from differently prepared... 

Various models of SFE have been published, which aim at understanding the kinetics of the processes. For many dynamic extractions of compounds from solid matrices, e.g. for additives in polymers, the analytes are present in small amounts in the matrix and during extraction their concentration in the SCF is well below the solubility limit. The rate of extraction is then not determined principally by solubility, but by the rate of mass transfer out of the matrix. Supercritical gas extraction usually falls very clearly into the class of purely diffusional operations. Gere et al. [285] have reported the physico-chemical principles that are the foundation of theory and practice of SCF analytical techniques. The authors stress in particular the use of intrinsic solubility parameters (such as the Hildebrand solubility parameter 5), in relation to the solubility of analytes in SCFs and optimisation of SFE conditions. 

The shrinking-core model (SCM) is used in some cases to describe the kinetics of solid and semi-solids-extraction with a supercritical fluid [22,49,53] despite the facts that the seed geometry may be quite irregular, and that internal walls may strongly affect the diffusion. As will be seen with the SCM, the extraction depends on a few parameters. For plug-flow, the transport parameters are the solid-to-fluid mass-transfer coefficient and the intra-particle diffusivity. A third parameter appears when disperse-plug-flow is considered [39,53],... 

In high pressure work, slurry reactors are used when a solid catalyst is suspended in a liquid or supercritical fluid (either reactant or inert) and the second reactant is a high pressure gas or also a supercritical fluid. The slurry catalytic reactor will be used in the laboratory to try different catalyst batches or alternatives. Or to measure the reaction rate under high rotational speeds for assessing intrinsic kinetics. Or even it can be used at different catalyst loadings to assess mass transfer resistances. It can also be used in the laboratory to check the deactivating behaviour. 

The first experiments reported here lead us to think that the impregnation of porous supports by drugs can be achieved by means of supercritical fluids. This one-step method yields a final product exempt from any residual trace of toxic solvent. The kinetics of the mass transfer is faster, besides the thermodynamics of the adsorption seems more favourable here. The main problem encountered up to now is the weak solubility of many active molecules in pure C02, which induces a limitation of the percentage of deposited product. However, this difficulty can be overcome by the use of few amount of an entrainer. In particular, ethanol which does not show any toxicity, would greatly extend the range of active substances which could be used. 

The effect of dissolved CO2 on the miscibility of polymer blends and on phase transitions of block copolymers has been measured with spectroscopy and scattering (40). The shifts in phase diagrams with CO2 pressure can be pronounced. Polymer blends may be trapped kinetically in metastable states before they have time to phase separate. Metastable polymer blends of polycarbonate (PC) and poly(styrene-cn-acrylonitiile) were formed with liquid and supercritical fluid CO2 in the PCA process, without the need for a surfactant. Because of the rapid mass transfer between the CO2 phase and the solution phase, the blends were trapped in a metastable state before they... 

All SFC processes operate at above the critical temperature (Tc) of supercritical fluids. Temperature is a critical controlling variable of the SFC process based on both thermodynamic and kinetic considerations. First, solubility is a function of temperature, and this will determine the supersaturation ratio or the driving force for the crystallization of individual polymorphs. Second, the kinetics of polymorphic transformation is governed by the Arrhenius law and is also temperature dependent. The rate constant of the conversion is related to the activation energy and the mass transfer process involved (i.e., diffusion, evaporation, or mixing in supercritical fluids). 

There are several reasons for carrying out reaetions in the supercritical phase. Naturally, some of the reasons are eoupled. Nevertheless, they, in general, relate to control, favorable mass transfer and kinetic considerations. 

Spinodal decomposition is of fundamental importance in processes involving phase separation of polymers in near- and supercritical fluids [145]. Pressure-induced phase separation (PIPS) has recently been used [4], with a novel experimental apparatus [146] that permits the imposition of rapid and controlled multiple pressure quenches, to study spinodal decomposition of near- and off-critical mixtures of a polymer and a compressed solvent following deep quenches into the unstable region. Spinodal decomposition is also important in SAS, in situations where the mass transfer pathway leads to penetration into the unstable region [76,147,148]. It can also be important in RESS involving polymeric solutes [35]. Experimental aspects of spinodal decomposition and the kinetics of phase separation in polymer solutions in near-critical fluids are discussed in the chapter by E. Kiran in this volume. 

King, J.W., Cygnarowicz-Provost, M., and Favati, F. (1997) Supercritical fluid extraction of evening primrose oil Kinetic and mass transfer effects. Ital. J. Food Set. 9, 193-204. 

King, J. W., M. Cygnarowicz-Provost, and F. Favati. 1997. Supercritical Fluid Extraction of Evening Primrose Oil Kinetic and Mass Transfer Effects. Italian Journal of Food Science 9 (3) 193-204. 

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