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Abstract: Supercritical fluids (SCFs) are powerful solvents with many unique properties. They have great potential for many processes, from extraction to chemical reactions and recycling. Accordingly, phase equilibrium data and thermodynamic and transport properties measurements in systems with a supercritical phase, as well as reliable and versatile mathematical models of the phase equilibrium thermodynamics, are needed for the process design and economic feasibility studies. The dissertation focuses on the benefits of supercritical fluid technology and consists of three main sections. The first section includes studies of the phase equilibria of the binary gas-alcohol and gas-urea derivatives. The influence of pressure and temperature on the system behaviour (solubility, viscosity, density, interfacial tension, melting point curve) was investigated. Most of the experiments were carried out with a high-pressure optical view cell, with minor modifications of the apparatus and measurement principle to determine mentioned thermodynamic and transport properties. The second part of the dissertation deals with the recovery of extracts from natural materials. Special interest is oriented towards supercritical fluid extracts, characterised by strong biological activities, especially antimicrobial and antioxidant properties. Supercritical fluid extraction has been performed on a semi-continuous apparatus (at pressures of 150 bar and 250 bar and temperatures of 313.15 K and 333.15 K for oregano extraction; and at pressures of 100 bar and 300 bar and temperatures of 313.15 K and 333.15 K for red beetroot extraction) and various methods such as the microdilution method and the DPPH method were used to determine antimicrobial and antioxidant activity. In the third part, an overview of different methods for recycling carbon fibre reinforced composites is given, including chemical recycling with supercritical fluids. This field has not been well explored, and the approach is relatively new but very interesting from a sustainable point of view. For an economically feasible process design, the thermodynamic and mass transfer data have to be determined. The principles of the future lab- and pilot-scale operations demand these supporting data be known. The results obtained in the frame of this study represent the high added value in the scientific field. They are essential to design and modify processes that yield products that cannot be achieved with conventional production processes.
Keywords: supercritical fluids, alcohols, urea, phase equilibria, viscosity, density, interfacial tension, modified capillary method, isolation methods, supercritical fluid extraction, pharmacological activity, carbon fiber reinforced composites, recycling techniques
Published in DKUM: 11.10.2022; Views: 582; Downloads: 111
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Abstract: The doctoral thesis presents the design of several high-pressure processes involving »green solvents« so-called supercritical fluids for the eco-friendly and sustainable production of new products with special characteristics, fewer toxic residues, and low energy consumption. The thesis is divided into three main parts: polymer processing and formulation of active drugs, measurements of transport properties form pendant drop geometry, and study of heat transfer under supercritical conditions. In the first part, special attention is given to using biodegradable polymers in particle size reduction processes that are related to pharmaceutical applications for controlled drug release. The PGSSTM micronization process was applied to the biodegradable carrier materials polyoxyethylene stearyl ether (Brij 100 and Brij 50) and polyethylene glycol (PEG 4000) for the incorporation of the insoluble drugs nimodipine, fenofibrate, o-vanillin, and esomeprazole with the purpose of improving their bioavailability and dissolution rate. In order to optimize and design micronization process, preliminary transfer and thermodynamic experiments of water-soluble carriers (Brij and PEG)/ SCFs system were carried out. It was observed that a combination of process parameters, including particle size reduction and interactions between drugs and hydrophilic carriers, contributed to enhancing the dissolution rates of precipitated solid particles. In the second part, a new optimized experimental setup based on pendant drop tensiometry was developed and a mathematical model designed to fit the experimental data was used to determine the diffusion coefficients of binary systems at elevated pressures and temperatures. Droplet geometry was examined by using a precise computer algorithm that fits the Young–Laplace equation to the axisymmetric shape of a drop. The experimental procedure was validated by a comparison of the experimental data for the water-CO2 mixture with data from the literature. For the first time, interfacial tension of CO2 saturated solution with propylene glycol and diffusion coefficients of propylene glycol in supercritical CO2 at temperatures of 120°C and 150°C in a pressure range from 5 MPa, up to 17.5 MPa were measured. Additionally, the drop tensiometry method was applied for measuring systems that are of great importance in carbon sequestration related applications. The effect of argon as a co-contaminant in a CO2 stream on the interfacial tension, diffusion coefficients, and storage capacity was studied. In the third part, comprehensive investigation into the heat transfer performance of CO2, ethane and their azeotropic mixture at high pressures and temperatures was studied. A double pipe heat exchanger was developed and set up to study the effects of different operating parameters on heat transfer performance over a wide range of temperatures (25 °C to 90 °C) and pressures (5 MPa to 30 MPa). Heat flux of supercritical fluids was measured in the inner pipe in the counter-current with water in the outer pipe. For the first time, the heat transfer coefficients (HTC) of supercritical CO2, ethane and their azeotropic mixture in water loop have been measured and compared. A brief evaluation is provided of the effect of mass flux, heat flux, pressure, temperature and buoyancy force on heat transfer coefficients. Additionally, to properly evaluate the potential and the performance of azeotropic mixture CO2-ethane, the coefficients of performance (COP) were calculated for the heat pump working cycle and compared to a system containing exclusively CO2.
Keywords: supercritical fluids, PGSSTM, formulation of active drugs, biodegradable polymers, transport and thermodynamic data, pendant drop method, carbon sequestration, heat transfer coefficients
Published in DKUM: 28.05.2018; Views: 1442; Downloads: 216
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Abstract: Non-woven cellulose material was functionalized using two techniques, i.e. the coating with AgCl via sol-gel and oxygen plasma. The treatment effects were studied regarding the wound fluid adsorption potential using physiological saline, synthetic exudate and synthetic blood. Plasma treatment was most efficient since a significant improvement by absorbency rate and capacity was evident, less pronounced in case of synthetic blood. The combination of both treatments showed a similar trend, while the effects were less prominent, but still sufficient by managing fluid-associated as well as infected wounds.
Keywords: non-woven cellulose fabric, sol-gel, oxygen plasma, absorption, synthetic wound fluids
Published in DKUM: 31.08.2017; Views: 1235; Downloads: 385
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Abstract: The influence of process parameters on supercritical fluid chromatography (SFC) and scale-up on to the preparative scale was investigated. In this scope, dependency of pressure, temperature, type and concentration of modifier, and type of stationary phase on the separation were examined separately. Experiments were performed on silica stationary phases in the range of pressures from 100 bar to 250 bar and temperatures from 30°C to 65°C, with use of ethanol and methanol as modifier. Results obtained on analytical scale were used for scale up on preparative (to production) scale. The aim of this study is presentation of the state-of-the-art of SFC through separate effects of process parameters on the separation and investigation of development, benefits and drawbacks of scaling-up process of the SFC.
Keywords: supercritical fluids, supercritical fluid chromatograpy, chromatography, scale up study, SFC
Published in DKUM: 21.12.2015; Views: 1435; Downloads: 152
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Keywords: carbon dioxide, equations of state, hydrogen, supercritical fluids
Published in DKUM: 10.07.2015; Views: 1204; Downloads: 29
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