Thesis (MTech (Environmental Management))--Cape Peninsula University of Technology, 2018. / South Africa is taking a continental lead towards the transition of the green economy, and the energy sector has been identified as one of the cornerstones integral in this transition. This transition pays attention to alternative energy sources to gradually replace fossil fuels. Recently, the production of ethanol is seen as an energy source that is an integral player in achieving a green economy. The ethanol production project is linked to the improvement of the economy, and social well-being concomitant with the enhancement of the environmental quality tenets embodied by the green economy. Scholars have noted that these projects tend to ignore socio-economic realities of under privileged people especially in rural areas and small towns. While the green energy is often presented by the state there is, however, no evidence of the positive as well as negative impacts of ethanol projects on improving the livelihoods of the local communities or contributing to the substance of the local economies while protecting the quality of the environment. This thesis explored the subject of ethanol projects as green economic models in the context of the ethanol project in Cradock. The thesis investigated the socio-economic implications of the ethanol project in Cradock as a green economic model. The research study argues that the inclusion of the local people in decision making for the ethanol project is crucial to securing their benefits from the project. This means that local people should be involved early in the decision making process. Failure to engage the local residents in the initial stages of decision making, may create a lack of sense of ownership resulting in a lack of socio-economic benefits for the residents. The research study adopted a qualitative research design and an inductive approach. The ethanol project in Cradock was used as a case study for the research, and two sampling techniques, purposive sampling and random sampling were used. Interviews, questionnaires and observations were used to collect data from the residents of Cradock, the business sector (hospitality, tourism and agricultural retail), the emerging farmers, the farm workers, the Agrarian Research Development Agency, and Government Departments (Local Economic Development, Department of Agriculture, Department of Rural Development and Land Reform). The findings illustrate that the ethanol project in Cradock is not consistent with the tenets of a green economic model. The results suggested that the project does not improve the livelihood of the community or contribute to the sustenance of the local economies while protecting the quality of the environment. From an environmental perspective, while the ethanol project regarding providing ethanol fuel contributes positively to the global green agenda, it deteriorates the quality of the local environment. The project pollutes the local environment which is a source of livelihood for the local people and the economy. Therefore, the adverse effect of the project on the local environment contributes to a negative effect on the local economy and livelihood of the residents. The results also revealed that the project stakeholders, particularly the residents of Cradock and the emerging farmers, were not involved in the early stages of the project where the benefits were determined. As a result, the stakeholders do not have a sense of ownership of the project, and there are uncertainties about the sustainability of their socio-economic benefits. The ethanol project introduces a shift from the traditional commercial agriculture to the production of biofuel feedstock. This causes an effect on the local economy and livelihood because traditional commercial agriculture has sustained the town for more than 200 years. The thesis raises questions about the notion that ethanol projects are green economic models.

Research project submitted in fulfillment of the academic requirements for the Masters Degree in Technology: Chemical Engineering, Durban University of Technology, 2010. / Globally there is renewed interest in the production of alternate fuels in the form of bioethanol and biodiesel. This is mainly due to the realization that crude oil stocks are limited hence the swing towards more renewable sources of energy. Bioethanol and biodiesel have received increasing attention as excellent alternative fuels and have virtually limitless potential for growth. One of the key processing challenges in the manufacturing of biofuels is the production of high purity products. As bioethanol is the part of biofuels, the main challenge facing bioethanol production is the separation of high purity ethanol. The separation of ethanol from water is difficult because of the existence of an azeotrope in the mixture. However, the separation of the ethanol/water azeotropic system could be achieved by the addition of a suitable solvent, which influences the activity coefficient, relative volatility, flux and the separation factor or by physical separation based on molecular size. In this study, two methods of high purity ethanol separation are investigated: extractive distillation and pervaporation. The objective of this project was to optimize and compare the performance of pervaporation and extraction distillation in order to produce high purity ethanol. The scopes of the investigation include:  Study of effect of various parameters (i) operating pressure, (ii) operating temperature, and (iii) feed composition on the separation of ethanol-water system using pervaporation.  Study the effect of using salt as a separating agent and the operating pressure in the extractive distillation process. The pervaporation unit using a composite flat sheet membrane (hydrophilic membrane) produced a high purity ethanol, and also achieved an increase in water flux with increasing pressure and feed temperature. The pervaporation unit facilitated separation beyond the ethanol – water system azeotropic point. It is concluded that varying the feed temperature and the operating pressure, the performance of the pervaporation membrane can be optimised. v The extractive distillation study using salt as an extractive agent was performed using the low pressure vapour-liquid equilibrium (LPVLE) still, which was developed by (Raal and Mühlbauer, 1998) and later modified by (Joseph et al. 2001). The VLE study indicated an increase in relative volatility with increase in salt concentration and increase in pressure operating pressure. Salt concentration at 0.2 g/ml and 0.3 g/ml showed complete elimination of the azeotrope in ethanol-water system. The experimental VLE data were regressed using the combined method and Gibbs excess energy models, particular Wilson and NRTL. Both models have shown the best fit for the ethanol/water system with average absolute deviation (AAD) below 0.005. The VLE data were subjected to consistency test and according to the Point test, were of high consistency with average absolute deviations between experimental and calculated vapour composition below 0.005. Both extractive distillation using salt as an extractive agent and pervaporation are potential technologies that could be utilized for the production of high purity ethanol in boiethanol-production.

Various methods for the production of bioethanol using different feedstocks have been researched on. In most work on bioethanol synthesis from sugar cane, tops and leaves have been regarded as waste and generally removed and thrown away. In this work, lignocellulosic sugarcane leaves and tops were not discarded but instead used as biomass to evaluate their hydrolyzate content. The leaves and tops were hydrolysed using different methods, namely concentrated acid, dilute acid pre-treatment with subsequent enzyme hydrolysis and compared with a combination of oxidative alkali pretreatment and enzyme hydrolysis. Subsequent fermentation of the hydrolyzates into bioethanol was done using the yeast saccharomyces cerevisae. Acid hydrolysis has the problem of producing inhibitors, which have to be removed and this was done using overliming with calcium hydroxide and compared to sodium hydroxide neutralization. Oxidative alkali pre-treatment with enzyme hydrolysis gave the highest yields of fermentable sugars of 38% (g/g) using 7% (v/v) peroxide pre-treated biomass than 36% (g/g) for 5% (v/v) with the least inhibitors. Concentrated and dilute acid hydrolysis each gave yields of25% (g/g) and 22% (g/g) yields respectively although for acid a neutralization step was necessary and resulted in dilution. Alkaline neutralization of acid hydrolyzates using sodium hydroxide resulted in less dilution and loss of fermentable sugars as compared to overliming. Higher yields of bioethanol, 13.7 (g/l) were obtained from enzyme hydrolyzates than 6.9 (g/l) bioethanol from dilute acid hydrolyzates. There was more bioethanol yield 13.7 (g/l) after 72h of fermentation with the yeast than 7.0 (g/l) bioethanol after 24h. However, the longer fermentation period diminishes the value of the increase in yield by lowering the efficiency of the process.

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. / Increasing global energy demand as well as air quality concerns have in recent years led to the search for alternative clean fuels to replace fossil fuels. One such alternative is the blending of petrol (gasoline) with ethanol, which has numerous advantages such as ethanol’s ability to act as oxygenate thus reducing the carbon monoxide emissions from the exhaust of internal combustion engines of vehicles. However, the hygroscopic nature of ethanol is a major concern in obtaining a perfectly homogenized petrol-ethanol fuel. This problem has led to the study of ways of homogenizing the petrol-ethanol mixtures. Therefore, this thesis aimed at enhancing the homogenization of petrol-ethanol mixture. Ethanol concentration in ethanol-water mixture plays a key role in enhancing the homogenization of the fuel, thus the bioethanol employed in this study was dehydrated with silica gel using ultrasonication-enhanced adsorption. Afterwards, the dehydrated ethanol was used in studying the homogenization of the fuel blend. Water removal from the bioethanol using ultrasonication-enhanced adsorption shows a 28% increase when compared to the water removal using magnetic-stirring-enhanced adsorption, During ultrasonication-enhanced adsorption, the estimated adsorption enthalpy was – 1 592.82 J/mol (exothermic) and the entropy was -5.44 J/ K mol, indicating a non-ordered loading of water molecules in the adsorption site. In addition, a modified pseudo second order kinetic model given by was proposed for the ultrasonication-enhanced adsorption process. Effect of temperature during ultrasonication-enhanced adsorption was found to be directly proportional to the amplitude and the pulse rate. However, increase in the amplitudes at lower pulse rates resulted in better cavitation, and hence better adsorption. Furthermore, during phase behavior of ethanol-petrol blend, volume fractions of ethanol and petrol were studied with respect to t the depth within the storage container to confirm homogenization of the blend and time of storage. The binodal curve of the ternary diagram shows an increase of homogeneous region indicating an improved interaction between water and petrol. Therefore, the interesting results regarding the homogenization of the fuel blends resulted from using ultrasonication-enhanced blending were very promising, and could be a platform upon which further research efforts could be built on. The concentration distribution in the reactor showed proof of cavitation formation since in both directions, the variation of concentration with both time and distance was found to be oscillatory. On comparing the profiles in both directions, the concentration gradient, diffusion flux, and energy and diffusion rates were found to be higher in the vertical direction compared to the horizontal direction. It was therefore concluded that ultrasonication creates cavitation in the mixture which enhances mass transfer and mixing of ethanol and petrol. The horizontal direction was found to be the diffusion rate limiting step which proposed that the blender should have a larger height to diameter ratio. It is however recommended that further studies be done on the rate-limiting step so as to have actual dimensions of the reactor. Testing of the blended fuel in internal combustion engine showed an optimal performance of this fuel at 60 % volume ethanol content with higher fuel power. The results of fuel consumption and emissions (such as CO2 and CO) trends confirm various reports in literature on the performance of ethanol/petrol blended fuel.

Commercial activated carbon and newly polymer-derived carbon were utilized to selectively remove the model fermentation inhibitor, furfural, from water solution during bio-ethanol production. Morphology, pore structure and surface chemistry of the sorbents were characterized. The oxygen groups on the carbon surface were believed to have contributed to the decrease on the selectivity of activated carbon between furfural and sugars (Sugars are the valuable source of bio-ethanol production and should not be separated from solution). Oxidization of activated carbon by nitric acid generated more information which supports the above assumption. Different adsorption isotherm models and kinetic models were studied to fit commercial activated carbon and polymer-derived carbon individually. Bacterial cell growth, sugar consumption, and ethanol yield during the fermentation were investigated after inhibitors were selectively removed from the broth. The fermentation time was reduced from one week to one day after inhibitor removal. Different methods of sorbent regeneration were investigated, including thermal regeneration, pH adjustment and organic solvent stripping. Low ethanol-containing water solution appears to be the most cost-effective way to regenerate the spent sorbent in the industrial application. A sorption/desorption cycle was designed and the sorbents were regenerated in a fixed-bed column system using ethanol-containing liquid from fermentation. The results were stable after running 20 times of sorption/desorption cycle.

Thesis (Ph.D)--Chemistry and Biochemistry, Georgia Institute of Technology, 2010. / Committee Chair: Ragauskas, Arthur; Committee Member: Bunz, Uwe; Committee Member: Deng, Yulin; Committee Member: Singh, Preet; Committee Member: Soper, Jake. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph.D.) - University of St Andrews, October 2009.

Submitted in fulfilment of the requirements for the degree of Masters of Science in Medicine in the Health Science Faculty University of Witwatersrand Johannesburg 10 April 2019 / The Forensic Chemistry Laboratories in South Africa have, between the year 2014 and 2017, endured a lot of media scrutiny surrounding a backlog of specimens for blood alcohol and toxicology analyses and the poor environmental and storage conditions in which these specimens are kept. Many studies have been performed on the stability of alcohol in blood, since environments are not standard, to gain a better understanding on whether the backlog issues significantly impact on the integrity of the blood-alcohol concentration (BAC) results by evaluation of conditions, especially variables such as temperature and headspace. The aim of this study was therefore, to assess the stability of ethanol concentrations in post-mortem blood specimens by evaluating temperature (room and refrigerator) and headspace (4mL and 8mL) variables at 3 months and 6 months respectively. Blood from 119 decedents was collected, analysed and subjected to the varied volumes and storage conditions. Blood alcohol was determined and quantified using a G1888 Headspace Auto sampler (Agilent Technologies®) coupled to a 6890N Agilent® Gas Chromatography instrument utilising a Flame Ionization Detector on an Agilent HP-Innowax® column. A general decrease in alcohol concentration was observed over a storage period of 6 months regardless of the storage temperature, whilst headspace was found to have no significant effect on the BAC results. It is, therefore, important that Forensic Pathologists, investigators and scientists are aware of factors such as temperature and headspace and consider them when interpreting blood alcohol results from a post-mortem environment. / E.K. 2019

Thesis (M.Sc. (Eng.))--University of the Witwatersrand, Faculty of Engineering and the Built Environment, School of Chemical and Metallurgical Engineering, 2016. / The world is gradually shifting to renewable clean energy and away from fossil fuels which are considered to have a finite reserve and have negative impact on the environment. Many alternatives have been developed including biofuels. Of the biofuel family, not all products are produced at the same level given the differences in technological advancements. Commonly produced biofuels which are commercialised are bioethanol and biodiesel. Given that a large number of vehicles operate using gasoline, there is a need to develop biogasoline specific processes to produce biogasoline. Bioethanol is used as a blending agent and has a drawback of engine corrosion. Biogasoline can be used for blending or to substitute gasoline in existing motors. The main objective of the project was to produce biogasoline from waste cooking oil using nano-particle catalyst for better performance. A Co-Mo/Al2O3 catalyst was synthesized and tested in two processes namely thermal cracking and hydrocracking. The waste cooking oil used in this study was pre-treated to remove salts and excess water prior to cracking process. Various analytical techniques were then used to characterize the catalyst, waste cooking oil and the products. Waste cooking oil was successfully pre-treated for salt removal with salt dropping from 13.18% to 4.37%. Effect of catalyst performance on thermal cracking proved to be minimal with temperature being the major factor in cracking. The catalyst performed better under hydrocracking with effects of catalyst calcination temperature and catalyst/oil ratio being more apparent as opposed to thermal cracking. Highest percentage biogasoline achieved under thermal cracking was 81.6% at a reaction temperature of 600°C. The highest percentage biogasoline achieved under hydrocracking was 75.7% at a reaction temperature of 210°C, using calcined catalyst at 700°C, catalyst/oil mass ratio of 1/75 and reaction time of 1hr. The biogasoline produced had low sulphur content. The highest sulphur containing product for hydrocracking was 7.4% and that for thermal cracking was 1.3%. It is recommended that the hydrocracking and thermal cracking methods be used for biogasoline production and that further research be done on the optimization of the biogasoline production process and synthesis of nano Co-Mo catalyst. / MT2016

The first part of the thesis presents a study based on the forest biorefinery concept, which involves converting a pulp mill into a multi-purpose biofuels, biomaterials, and biopower production facility in which these products are produced in an environmentally compatible and sustainable manner. A key challenge in this process is the recovery of lignin from process streams such that it can be utilized in a variety of innovative green chemistry processes The first study examines the fundamental chemical structure of LignoBoost derived lignin recovered from Kraft pulping streams using an acid precipitation/washing methodology. Functional group analysis and molecular weight profiles were determined by nuclear magnetic resonance (NMR) and size exclusion chromatography. These findings gave valuable insight into the physical properties and the determining chemical properties of this currently underutilized, renewable bioresource. The second study is based on the future second generation bioethanol production process, where ethanol produced from lignocellulosic materials will bring about the co-production of significant amounts of under-utilized lignin. The study examines the potential of conventional heterogeneous and novel homogeneous catalysts for the selective cleavage of the aryl-O-aryl and aryl-O-aliphatic linkages of ethanol organosolv lignin to convert it from a low grade fuel to potential fuel precursors or other value added chemicals. The experimental data demonstrated that aryl-O-aryl and aryl-O-aliphatic linkages could be cleaved and the hydrogenated lignin had a decrease in oxygen functionality and the formation of products with lower oxygen content. The second part of this thesis reports the development and optimization of a novel qualitative method for the determination of the various types of hydroxyl groups present in biodiesel production streams. In the first study, the use of 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane as a phosphitylation reagent for quantitative ³¹P-NMR analysis of the hydroxyl groups in biodiesel process samples has been developed. Subsequently a characteristic chemical shifts library is developed with model compounds to provide quantitative data on the concentration of biodiesel precursors, intermediates and final product. The last part of this thesis depicts the results of an industrial trial based on the novel biodiesel analytical method developed earlier.