Development of a dynamic still for measuring low pressure vapour-liquid-liquid equilibria : systems of partial liquid miscibility.

Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2005.The dynamic still originally designed by Raal (Raal and Muhlbauer [1998]) has been transformed into a valuable still that can now be used for measuring both low pressure vapour-liquid equilibria (VLE) for systems that are completely miscible and vapour-liquid-liquid equilibria (VLLE) for systems that are partially miscible. The resultant equilibrium data are important in the design and analysis of distillation and allied separation process equipment, with VLLE data, in particular, being useful in the design of heterogeneous azeotropic distillation columns. The original Raal still was based on the designs of Heertjies [1960] and Yerazunis [1964], who successfully used a packed equilibrium chamber where the liquid and vapour phases are forced downward co-currently to achieve rapid and dynamic equilibrium (Joseph et al [2001]). Direct analysis of the vapour composition prior to condensation through a new heated valving system with superheated sample conveyance to a gas chromatograph, a modification incorporated into the Raal still, ensured that accurate and reproducible equilibrium data were obtained. This new arrangement dispenses with the impossible task of getting the actual vapour composition that would result were the vapours allowed to condense and form two liquid phases. The initial testing of the still which established the operating procedures was conducted on two previously measured systems - the first which was homogeneous and the second heterogeneous. For the homogeneous system the new vapour sampling system was tested by comparing the measured composition to that of a condensed sample sent manually to the GC using a gas-tight syringe. In order to completely describe the VLLE for the systems studied, the liquid-liquid equilibrium (LLE) data for these systems were also measured. The LLE measurements were conducted in a newly-developed small jacketed glass cell with temperatures maintained constant by circulating water from a bath maintained at the desired temperatures. The main focus of this project was thus the development of an apparatus and procedures for measuring low pressure vapour-liquid-liquid equilibria. The project also went on to measuring and modeling VLE, VLLE and LLE data for selected binary and ternary systems. Both the Gamma-Phi and the Phi-Phi methods of VLE analysis were carried out on the measured data. The NRTL, Wilson, TK-Wi1son and UNIQUAC activity coefficient models were used in the Gamma- Phi method together with the Virial equation of state for vapour phase non-idealities. In the Phi-Phi method, The Peng and Robinson Equation of State (EOS), the Soave Redlich-Kwong EOS and the Stryjek and Vera modified Peng and Robinson EOS were all used, first with the classical mixing rules and then with the theoretically correct Wong and Sandler [1992] mixing rules. Ternary LLE binodal curves were correlated to the Hlavaty correlation, the beta function and the log gamma function while the corresponding tie-lines were fitted to the NRTL model