A study has been made using computer simulation of a fractionating column with simultaneous distillation and chemical reaction occurring. The assumptions of 100% efficient trays and ideality of vapor-liquid equilibrium and thermal properties were made. Results show that the extent to which a reversible reaction can be driven, or an irreversible side reaction inhibited, is a strong function of the ease with which the reaction products may be removed using the separating capacity of the fractionating column. The quantity of liquid holdup per plate is also a factor of considerable importance in the performance of a fractionating column with chemical reaction, but its effect is not simple, interacting as it does with the reflux ratio. The effect of system pressure is complex. Increasing pressure raises temperatures, and therefore reaction rates but decreases separation factors. The influence of this with respect to the main reaction and any undesirable side reactions is so specific to the chemical reaction being studied that no overall generalization can usefully be made. Considering only the point of view of the amount of reaction achieved, a fractionating column can show considerable improvement over a continuous stirred tank reactor. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Submitted in fulfillment of the requirements for the degree of Master of Engineering, Durban University of Technology, Durban, South Africa, 2015. / There are various types of separation processes used in industries, such as, distillation, liquid-liquid extraction and gas absorption. Liquid-liquid extraction (LLE) is a separation process that involves mass transfer from a liquid mixture to an immiscible extraction solvent. This process is generally used where the mixture cannot be separated by fractional distillation due to close relative volatilities of the mixture components or for heat sensitive components. LLE is rated as the second most important separation process after distillation and it is widely used in chemical engineering industries. Different types of columns are available for LLE. Reciprocating and vibrating plate extraction columns are mechanically agitated extraction columns. In this research a vibrating plate extraction column was utilised. It uses perforated plates with down-comers. The perforations provide passage for the dispersed phase, while down-comers provide passage for the continuous phase. The effectiveness of a vibrating plate extractor was previously investigated but limited research was conducted on the effect of the different tray designs and agitation levels (as the product of amplitude and frequency of vibration). These variables affect the hydrodynamics and mass transfer in the column. The determination of the optimum process parameters is important in achieving the highest separation efficiency of the vibrating extraction column. The focus of this research is to test the effect of different tray designs in order to enhance the separation process efficiency. All tests were conducted using the toluene-acetone-water system as a standard test system proposed by the European Federation for Chemical Engineering, (1985). The experiments were conducted to test the effect of mass transfer on the hydrodynamics of the system while changing the agitation levels, downcomers and hole diameters. A comparative investigation was conducted on straight segment and circular downcomers, then hole diameters analysis was performed on the effective downcomer Comparison of the effect of the tray design types on the amount of acetone extracted was utilised to select the effective tray. Tray with the circular downcomer and 3.0 mm hole diameter had high dispersed phase holdup values and with the highest percentage amount of acetone extracted (95.05%) was obtained compared to other tray designs investigated.

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. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2005.