Modelowanie procesów wytwarzania proszków przy użyciu płynów w stanie nadkrytycznym

• Autorzy: Henczka M.

Warianty tytułu

EN

Modelling of particle formation processes using supercritical fluids

• Języki publikacji: PL

Abstrakty

PL

Przedmiotem pracy są metody opisu matematycznego przebiegu procesu wytwarzania proszków do zastosowań medycznych przy użyciu płynów w stanie nadkrytycznym. Charakterystyczną cechą rozważanej grupy technologii jest silna zależność własności otrzymywanych cząstek stałych od warunków oraz sposobu prowadzenia procesu precypitacji. Pozwala to na sterowanie przebiegiem produkcji proszków w celu otrzymania produktu o wymaganych własnościach poprzez odpowiedni dobór parametrów procesowych. W pierwszej części pracy przedstawiono krótki przegląd i ocenę technologii płynów w stanie nadkrytycznym w kontekście ich użyteczności do bezpiecznego i kontrolowanego przetwarzania farmaceutyków. W przeglądzie tym przedyskutowano zalety, niedoskonałości i ograniczenia zastosowań poszczególnych metod. Następnie omówiono własności fizykochemiczne płynów w stanie nadkrytycznym i mieszanin z ich udziałem oraz usystematyzowano zależności użyteczne do modelowania tych własności. Przedstawiono także metody opisu równowag fazowych w układach dwu- i trójskładnikowych, w których prowadzi się procesy wytwarzania proszków. W dalszej części pracy rozważono szczegółowo dwie technologie wytwarzania proszków w przemyśle farmaceutycznym. Pierwsza z nich polega na wykorzystaniu zjawiska obniżania rozpuszczalności związków chemicznych w rozpuszczalnikach organicznych przez dodatek płynu w stanie nadkrytycznym. Opis procesu wymaga wykorzystania metod modelowania przebiegu procesów precypitacji z roztworów wodnych w połączeniu zarówno z opisem złożonych zależności termodynamicznych charakteryzujących płyny ściśliwe, jak i ze specyficznym opisem przepływu i mieszania burzliwego. Kluczowym elementem tej części pracy jest metoda zamknięcia równań bilansowych opisujących przebieg procesu precypitacji przy użyciu płynów w stanie nadkrytycznym. Do modelowania własności produkowanych proszków zastosowano procedurę rekonstrukcji rozkładu rozmiaru cząstek. Druga rozważana metoda stanowi połączenie procesu zamrażania rozpyłowego z suszeniem próżniowym i jest stosowana do bezpiecznej produkcji sproszkowanych substancji bioaktywnych. Polega ona na jednoczesnej atomizacji i zamrażaniu wodnego roztworu wytrącanej substancji w wyniku szybkiego rozprężenia silnie sprężonej mieszaniny dwufazowej zawierającej dwutlenek węgla w stanie ciekłym lub nadkrytycznym. W tej części pracy opracowano metodę opisu wpływu burzliwości przepływu i rozprężania mieszaniny na przebieg procesów dyspersji oraz zamarzania kropel roztworu wodnego. Zaproponowana metoda modelowania przebiegu procesu nie wymaga stosowania stałych dopasowujących wyniki obliczeń do danych doświadczalnych, co świadczy o jej uniwersalnym charakterze. Wynikiem niniejszej pracy jest opracowanie metod opisu matematycznego przebiegu procesów wytwarzania proszków dla dwóch technologii przemysłu farmaceutycznego. Zaproponowane modele matematyczne rozważanych procesów zostały zweryfikowane poprzez zastosowanie ich do interpretacji i przewidywania wyników badań doświadczalnych. Wykazano, że zastosowanie przedstawionych metod modelowania pozwala na przewidywanie wpływu warunków prowadzenia procesów precypitacji na własności wytwarzanych proszków. W aspekcie praktycznym wyniki niniejszej pracy mogą zostać wykorzystane jako narzędzia użyteczne do projektowania i optymalizacji technologii wytwarzania farmaceutyków w formie proszków.

EN

The work is focused on the methods of modellling in the influence of turbulence on the course of particle formation processes with the use of supercritical fluids (SCF). Application of supercritical fluid technologies enables production of ultrafine (micro- or nanosized) powders of high purity and narrow particle size distribution. Moreover, supercritical fluids are easily separated form crystalline products providing clean and recycable technologies. This causes that particle formation is presently considered one of the major developments of supercritical fluids technologies, mainly in the pharmaceutical, nutraceutical and cosmetic industries. In particular, the pharmaceutical industry aims at producing ultrafine particles to use as powderized drugs administered by various routes including inhalation and oral modes. As the first process, supercritical antisolvent precipitation is considered. The principle of this method relies in sharp decrease of the power of the liquid solvent by addition of a supercritical fluid in which the solute is insoluble. Particle size distribution of the solid product can be controlled by adjusting the rate of mixing of fluids, as well as the rate of addition of the antisolvent. Depending on the process conditions, the resulting mixture forms homo- of heterogeneous systems. The general model of antisolvent precipitation in turbulent field for homogeneous systems is presented. The method combines the non-equilibrium model for scalar dissipation with the conditional moment closure based on probability density function Beta (the Beta PDF). The main idea of the model is based on expressing the local concentration of the precipitated substance as a function of dimensionless concentration of the solvent interpreted as a passive scalar and application of the single precipitation progress variable. The presented PDF method has been verified experimentally. The results of numerical simulations have been compared with experimental data for precipitation of paracetamol from the ethanol solution with the use of carbon dioxide as an antisolvent. The second method considered in this work is spray-freezing with compressed carbon dioxide. The process is suitable for processing proteins, antibodies, vaccines, dry powder aerosols and nanoparticles. During the process, liquid droplets of the solution are first dispersed within supercritical CO2 and then frozen in Joule-Thomson's expansion cooling. The most important stage of the process directly determining the final particle size and structure atomization of the aqueous solution of the precipitated substance. The work is particulary focused on modelling the influence of turbulence on the course of aqueous droplet dispersion and solidification process. Two mechanisms of droplet breakup are taken into account, namely Rayleigh-Taylor instablities and activity of turbulent stresses. The proposed procedure enables indentification of the flow field of the mixture, the distribution of temperature of the dispersed phase and the position in the system where the droplet starts to freeze. Finally, the method enables to predict the average size of frozen droplets, which is comparable with the size of produced solid particles. In modelling complex processes of particle formation using supercritical fluids, the different aspects, such as thermodynamics, fluid dynamics and precipitation kinetics, are complementary and provide a comprehensive process description only when cosidered together. The mathematical models presented in this work after implementation into the commercial CFD software constitute complete numerical procedures useful for prediction of the course of particle formation processes. In practical applications, these methods can be applied in optimization and scaling-up of industrial supercritical fluid technologies.

Słowa kluczowe

PL

płyn w stanie nadkrytycznym; precypitacja; CFD; mikromieszanie; burzliwość

EN

supercritical fluid; precipitation; CFD; micromixing; turbulence

• Wydawca: Oficyna Wydawnicza Politechniki Warszawskiej
• Czasopismo: Prace Wydziału Inżynierii Chemicznej i Procesowej Politechniki Warszawskiej
• Rocznik: 2008
• Tom: Vol. 32, z. 3
• Strony: 3--202
• Opis fizyczny: Bibliogr. 333 poz., tab., rys., wykr.

Twórcy

autor

Henczka M.

• Zakład Mechaniki Technicznej i Dynamiki Procesowej

Bibliografia

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