.. Detailed experimental and thermodynamic studies of. the isothermal phase equilibria for the / Thesis (Ph.D.)-University of Natal, 1990.

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Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2009. / Full text also available online. Scroll down for electronic link.

The vapour recirculation apparatus of Moodley [2002] was modified, reconstructed, and commissioned in order to be used in the acquisition of high-pressure vapour-liquid equilibrium (HPVLE) data at low temperatures. The original equipment of Moodley [2002] was modified with the aim of achieving the desired operating temperature range which the original equipment was unable to achieve. Major modifications were carried out on the cooling circuit allowing the equipment to reach temperatures as low as -30°C, a significant improvement to the original equipments minimum attainable temperature of -5°C. Modifications were also successfully carried out on the vapour recirculation pump of Moodley [2002], which failed when operated over extended periods at high pressures thus enabling the equipment to operate at pressures up to 10.0 bar, an improvement on the previous pressure operating limit of 6.9 bar. The operating limits of the equipment were tested through measurement of pure-component vapour-pressures of isopentane at temperatures between -14 and +27.9°C and pressures up to 10.1 bar and on propane at temperatures between -30.1 and +26.0°C and pressures up to 9.7 bar. The isopentane vapour-pressure measurements had an average deviation of ±0.49% when compared to literature data while the propane vapour-measurements had a maximum average deviation of ±0.35% when compared to literature data indicating that the equipment was capable of measuring accurate vapour-pressure data at temperatures down to -30°C and pressures up to 10.0 bar. The equipment was thereafter used in the acquisition of binary HPVLE data. Considerable time was spent developing and practicing the techniques used in the binary HPVLE measurements. Binary measurements were performed on the test system propane + 1- propanol at 19.9°C. To gain more confidence in the binary HPVLE measurements another test system, propane + isopentane was selected and binary HPVLE measurements were performed at 25°C and 0°C. The equipment was able to reproduce relatively accurate binary HPVLE results for the test systems at the selected isotherms. The equipment was thereafter used in the acquisition of a new set of binary HPVLE data for the propane + isopentane system at -10°C however owing to time constraints and chemical availability the acquisition of a complete set of data was not possible. The binary HPVLE data was thereafter regressed via the direct method. The Peng-Robinson (PR) equation of state (EOS) and the Soave-Redlich-Kwong (SRK) EOS were each coupled with the Mathias Copeman alpha function together with the Wong-Sandler mixing rule and the NRTL local composition model and applied to the binary systems at each of the isotherms investigated. Regressed data showed a relatively good agreement with measured experimental data for both binary systems investigated at all of the isotherms except the new -10°C isotherm of the propane + isopentane system. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2010.

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High pressure vapour-liquid equilibrium experiments were undertaken with a static high-pressure apparatus designed by Prof. J. D. Raal and commissioned by Prof. D. Ramjugernath. Isothermal VLE binary data data was measured at moderate temperatures and pressures ranging from atmospheric to 7.2 bar. The equipment had a combined operating pressure and temperature limit of approximately 150 bar and 215° C respectively. The apparatus was initially designed for the measurement of gas-liquid binary systems- where one of the components was supercritical at the operating conditions. Test data were measured for the pentane + ethanol system at 100.41°C. The 2-methyl-2-butene + TAME, hydrocarbon + olefin system, was observed at 70°C, 94.6°C and 104.5°C. The apparatus was modified for the measurement of binary systems containing sub-critical components at the operating conditions specified. An injection port was installed on the apparatus assembly such that the second component of the binary system could be introduced into the equilibrium cell. The binary VLE data was regressed using various thermodynamic models. The direct method or phi-phi approach was considered. The equations of state models used in the regression were the Peng-Robinson-Stryjek-Vera (PRSV) and Soave-Redlich-Kwong (SRK). The 1-fluid van der Waals, Wong and Sandler mixing rules were selected to estimate binary interactions. The excess Gibbs energy equations coupled with the Wong and Sandler mixing rules were the NRTL and WILSON equations. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2009.

Phase equilibrium data are vital in process design for chemical industries. Development of / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, 2006.

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The South African based petrochemical company, SASOL, operates three large plants for the recovery and purification of the chemical 1-hexene. The thermodynamic models available in commercial simulation packages fail to predict or correlate the plant data presently observed by SASOL. The focus of this project is the accruement of comprehensive and accurate modelling parameters that would assist SASOL in optimizing the operation of the three plants and meet their purity specifications. The experimental requirements of the project are the measurement of isothermal vapour-liquid equilibrium (VLE) data for selected binary systems, using a dynamic still. The binary systems investigated were 1-hexene + n-methylpyrrolidone (NMP) at 40, 62 and 90 °C, water + NMP at 70, 90 and 107 °C and 1-hexene + 3methylcyclopentene (3MCP) at 40, 50 and 60 °C. With respect to the modelling of the VLE data, the combined (gamma-phi) and direct (phi-phi) regression procedures were utilized. The results of the analysis show the combined method as the more flexible of the two, when used for low pressure systems. The excess Gibbs energy correlations investigated were the Margules, Van Laar, Wilson, NRTL and UNIQUAC. The NRTL and Van Laar models dominated the modelling results across the range of temperatures for each binary system and for both the direct and combined methods of data regression. The experimental data for the systems of water (1) + NMP (2) at 107 °C and at 70 °C were compared to literature data. The first system showed excellent correlation with the literature results while the second plot at 70 °C showed a positive bias of the experimental data between xj of 0.3 and 0.8. Thermodynamic consistency tests for the VLE data are also required to verify the accuracy of the data. For this project, the point and direct (Van Ness) consistency tests were used as the area test was considered as too mild. All systems passed the point and direct tests for the combined method and therefore verify the thermodynamic consistency of the experimental data. The systems failed in most cases for the direct method as the combined method is the more flexible of the two modelling methods. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2007.

VLE data is essential for the design and optimisation of industrial separation processes. Carboxylic acids are of significant interest because of their importance in both industrial and biological processes. Carboxylic acids are used as raw materials for a wide range of products, which include soaps , detergents, nylon , biodegradable plastics, medical drugs and food additives, They are also used both as solvents and as additives and co solvents under a wide range of conditions. Carboxylic acids exhibit strong self and cross -association through hydrogen bonds in both liquid and vapour phases. A thorough understanding of how these molecules interact both with themselves and with other solvents becomes necessary if existing processes may be optimised and new processes developed. Vapour-liquid equilibrium (VLE) data were measured for carboxylic acid systems ranging from C3 to C6• New vapour-liquid equilibrium data were measured for the following binary carboxylic acid systems: • Propionic acid + Hexanoic acid at 20 kPa, 403.15 K, 408.15 K and 413.15 K. • Isobutyric acid + Hexanoic acids at 20 kPa, 413.15 K and 423.15 K. • Valerie acid + Hexanoic acid at 15 kPa, 423 .15 K and 433.15 K. • Hexanoic acid + Heptanoic acid at 10 kPa and 443.15 K. A highly refined dynamic VLE Still by Raal (Raal and Muhlbauer [1998]) was used to undertake the VLE measurements. The still was operated either isothermally or isobarically using a computer control scheme. The isobaric and isothermal control was measured to be ±0.03 kPa and ±0.02 K respectively. The experimental procedure was verified with the highly volatile cyclohexane (l) + ethanol (2) system. The cyclohexane (l) + ethanol (2) measured VLE data was found to be in good agreement with that of Joseph (2001) and passed both the direct test and point test for thermodynamic consistency. A high degree of confidence was then placed on the equipment set-up and experimental procedure, as well as the new carboxylic acids VLE data . The VLE data for all the systems measured were modelled. Two data reduction methods were used: I. The combined ( r- ¢ ) method u. The direct method (¢ - ¢ ) method. In the combined method, the vapour phase non-idea lity was corrected using the Pitzer-Curl (1957) correlation and the Hayden and O' Connell (1975) chemical theory approach. Three liquid phase activity coefficient models were used namely the Wilson, NRTL, and UNIQUAC equations. The Peng-Robinson equation of state (Peng and Robinson [1976]) in combination with the Twu and Coon mixin g rule was used in the direct method. Thermodynamic consistency tests were done on all the systems measured. The point test (Van Ness et a!. [1973]) and the direct test Van Ness ([ 1995]) were used for consistency tests . The direct test could not be carried out on the carboxylic acids data because of the model's inability to adequately characterise the experimental activity coefficients. Generally the models fitted the data well but failed to accurately predict the "S" shape of the carboxylic acids phase diagrams. Considerable work still exists for further investigation into carboxylic acids. Currently, many experimentalists are working in this area . Penget a!. (2004) present ed their progress on developing an equation of state incorporating chemical theory to specifically handle carboxylic acids at the ICCT conference in Beijing, 2004. Raal and Clifford (University of Kwa-Zulu Natal, Thermodynamics Research Unit) are currently developing activity coefficient models incorporating chemical theory for a binary mixture of carboxylic acids. This work is part of the continuing research to under stand the phase behaviour of carboxylic acids. / Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2005.