Submitted in fulfillment of the requirements of the degree of Master of Engineering, Durban University of Technology, Durban, South Africa, 2016. / Separation processes in the chemical process industries is dependent on the science of chemical thermodynamics. In the field of chemical separation process engineering, phase equilibrium is a primary area of interest. This is due to separation processes such as distillation and extraction which involves the contacting of different phases for effective separation. The focal point of this research project is the measurement and modeling of binary vapour-liquid equilibrium (VLE) phase data of systems containing ether-alcohol organic compounds. The VLE data were measured with the use of the modified apparatus of Raal and Mühlbauer, (1998). The systems of interest for this research arose from an industrial demand for VLE data for systems containing ether-alcohol organic compounds. This gave rise to the experimental VLE data isotherms being measured for the following binary systems: a) Methyl tert-butyl ether (1) + 1-pentanol (2) at 317.15 and 327.15 K b) Methyl tert-butyl ether (1) + 2, 2, 4-trimethylpentane (2) at 307.15, 317.15 and 327.15K c) 2, 2, 4-Trimethylpentane (1) + 1-pentanol (2) at 350.15, 360.15 and 370.15K d) Diisopropyl ether (1) + 2,2,4-trimethylpentane (2) at 320.15, 330.15 and 340.15K e) Diisopropyl ether (1) + 1-propanol (2) at 320.15, 330.15 and 340.15K f) Diisopropyl ether (1) + 2-butanol (2) at 320.15, 330.15 and 340.15K The data for all the measured binary systems investigated at these temperatures are currently not available in the open source literature found on the internet and in library text resources. The systems were not measured at the same temperatures because certain system isotherm temperatures correlate to a pressures above 1 bar. This pressure of 1 bar is the maximum operating pressure specification of the VLE apparatus used in this project. The experimental VLE data were correlated for model parameters for both the  and methods. For the method, the fugacity coefficients (vapour-phase non-idealities) were tabulated using the virial equation of state and the Hayden-O’Connell correlation (1975); chemical theory and the Nothnagel et al. (1973) correlation method. The activity coefficients (liquid phase non-idealities) were calculated using three local-composition based activity coefficients models: the Wilson (1964) model, the NRTL model (Renon and Prausnitz, 1968); and the UNIQUAC model (Abrams and Prausnitz, 1975). Regarding the direct method, the Soave-Redlich-Kwong (Redlich and Kwong, 1949) and Peng-Robinson (1976) equations of state ii were used with the temperature dependent alpha-function (α) of Mathias and Copeman (1983) with the Wong-Sandler (1992) mixing rule. Thermodynamic consistency testing, which presents an indication of the quality and reliability of the data, was also performed for all the experimental VLE data. All the systems measured showed good thermodynamic consistency for the point test of Van Ness et al. (1973) - the consistency test of choice for this research. This however, was based on the model chosen for the data regression of a particular system. Therefore, the combined method of VLE reduction produced the most favourable results for the NRTL and Wilson models. / M

The labelling of methyl tertiary butyl ether (MTBE), an oxygenate additive used extensively in gasoline blending, as an environmentally harmful chemical has led to the banning and subsequent phasing-out of this additive in California (USA). In response, the global petroleum industry is currently considering replacement strategies, which include the use of tertiary amyl methyl ether (TAME) or ethanol. Subsequently, SASOL (South African Coal and Oil Limited), a local petrochemical company, in its capacity as an environmentally responsible player in the global petroleum and aligned chemical markets, has commissioned this investigation into the environmental fate of the fuel oxygenates: TAME, ethanol and MTBE. In order to evaluate the environmental fate of the oxygenates, this dissertation has formed a three-tiered approach, using MTBE as a benchmark. The first tier assessed the general fate behaviour of the oxygenates using an evaluative model. A generic evaluative model, developed by Mackay et al. (l996a), called the Equilibrium Criterion (EQc) model was used for this purpose. This fugacity based multimedia model showed MTBE and TAME to have similar affinities for the water compartment. Ethanol was demonstrated to have a pre-disposition for the air compartment. Parameterisation of the EQC model to South African conditions resulted in the development of ChemSA, which reiterated the EQC findings. The second tier quantified the persistence (P), bioaccumulation (B) and long-range transport (LRT) potential of the additives. This tier also included a brief toxicity (T) review. MTBE and ethanol were demonstrated to be persistent and non-persistent, respectively, according to three threshold limit protocols (Convention on the Long Range Trans-boundary Air Pollution Persistent Organic Chemical Protocol; the United Nations Environment Programme Global Initiative; and the Track 1 criteria as defined by the Canadian Toxic Substances Management Policy, as referred to by the Canadian Environmental Protection Act 1999). These protocols were not unanimous in the persistence classification of TAME. Further investigation of persistence was conducted using a persistence and long-range transport multimedia model, called TaPL3, developed by Webster et al. (1998) and extended by Beyer et al. (2000). TaPL3 reiterated the conclusions drawn from the threshold limit protocols, indicating that TAME's classification worsened from non-persistent to persistent on moving from an air emission to a water emission scenario. This served to emphasise the negative water compartment affinity associated with TAME. Using classification intervals defined by Beyer et al. (2000), TaPL3 demonstrated that the long-range transport potential of the oxygenates increased in the order of TAME, ethanol and MTBE; however, it was concluded that none of the oxygenates were expected to pose a serious long-range transport threat. Bioaccumulation was not expected to be a pertinent environmental hazard. As expected, the oxygenates were dismissed as potential bioaccumulators by the first level of a screening method developed by Mackay and Fraser (2000); as well as by the threshold limit protocols listed above. Simulation of biomagnification, using an equilibrium food chain model developed by Thomann (1989), demonstrated that none of the oxygenates posed a biomagnification threat. A review of toxicity data confirmed that none of the three oxygenates are considered particularly toxic. LDso values indicated the following order of increasing toxicity: ethanol, MTBE and TAME. The third tier focussed on oxygenate aqueous behaviour. A simple equilibrium groundwater model was used to analyse the mobility of the oxygenates in groundwater. TAME was found to be 21 % less mobile than MTBE. Ethanol was shown to be very mobile; however, the applicability of the equilibrium model to this biodegradable alcohol was limited. An analysis of liquid-liquid equilibria comprised of oxygenate, water and a fuel substitution chemical was performed to investigate fuel-aqueous phase partitioning and the co-solvency effects of the oxygenates. Ethanol was shown to partition appreciably into an associated water phase from a fuel-phase. Moreover, this alcohol was shown to act as a co-solvent drawing fuel chemicals into the water phase. MTBE was found to partition sparingly into the water phase from a fuel-phase, with TAME partitioning less than MTBE. Neither ether was shown to act as a co-solvent. It was concluded that TAME and ethanol pose less of a burden to the environment than MTBE. Ethanol was assessed to be environmentally benign; however, it was concluded that ethanol's air compartment affinity and the extent of its co-influence on secondary solutes justified the need for further investigation before its adoption as a fuel additive. This project showed sufficient variation in the environmental behaviour of TAME and MTBE to justify the abandonment of the axiom that MTBE and TAME behave similarly in the environment. However, as MTBE is a significant water pollutant, and TAME has been shown to share a similar water affinity, it is cautiously recommended that the assumption of environmental similarity be discarded, except for the water compartment. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2002.