M.Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / This thesis presents a slight on desulphurization process of the commercial diesel fuel using the carbon-based metal oxide nanocomposites such as graphene oxide, ZnO, rGO as a nano-adsorbent, activated carbon (PAC and AC) and charcoal Granular active carbon (GAC) to produce a fuel of less than 10 ppm sulphur content. Due to the high percentage of sulphur compounds in the fuel causing air pollution, acid rain and other problems related to combustion process. The synthesised of sorbents were achieved using incipient impregnation, microwaved-assisted and chemical exfoliation methods. The materials were characterized using Thermogrametric Analyzer (TGA), Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometer (XRD), Brunauer, Emmett and Teller (BET). The examination effect of operating conditions on the adsorption capacity with DBT and Sulphur compounds adsorption, the isotherms and the adsorption kinetic models were evaluated. The experimental data for PAC and AC were well suited to Freundlich isotherm and pseudo second-order kinetic models. The results shown that the sulphur feed concentration, the space velocity and the functional groups of the adsorbents have a considerable effect on the adsorption. In addition, it was observed that the temperature in the range of 30 to 80oC has a significant effect on the adsorption of Sulphur compounds from diesel fuel using 20 wt.% of sorbents. The rGO substrate which contained abundant oxygen functional groups was confirmed to promote the dispersion metal oxide and increased the adsorption efficiency of sulphur compounds (H2S and SO2) by providing oxygen ions weakly bound to the sulphur molecules. For the desulfurization process by adsorption, PAC and AC exhibited a better affinity for 80% removal of sulphur compared to the GAC and GO. The effects of metal species such as zinc oxide (ZnO) and reduced graphite oxide (rGO) composite on the adsorption capacity of hydrogen sulphide (H2S) were investigated. It was found that depending on the copper load, the adsorption capacity of H2S increased up to 20 times compared to pure ZnO. To study the oxidation changes on copper and zinc oxides, crystallite analysis by XRD and chemical state analysis by XPS were performed.

Le nitrite est un ingrédient essentiel à la fabrication du jambon cuit, pourtant les risques sanitaires dont il est accusé remettent en question son utilisation. L’emploi de cet unique additif permet de remplir de nombreuses fonctions comme la protection antioxydante et antimicrobienne mais aussi le développement de la couleur et de l’arôme. C’est sur cette dernière fonction que ce travail de thèse s’est focalisé avec pour objectif la suppression du nitrite dans la fabrication du jambon cuit. La mise en œuvre de plusieurs techniques complémentaires de chromatographie en phase gazeuse couplées à l’olfactométrie a permis dans une première partie d’identifier le 2-methyl-3-furanthiol, 2-methyl-3-(methyldithio)furan, et le bis(2-methyl-3-furyl)disulfide comme les molécules soufrées responsables de l’arôme du jambon cuit. Il est apparu qu’en l’absence de nitrite et par conséquent en absence de protection antioxydante, les composés odorants issus de l’oxydation sont produits massivement et ont tendance à perturber l’arôme global du jambon cuit. Afin de restaurer l’arôme en l’absence de nitrite, l’étude a été organisée selon 2 axes : le premier visant à favoriser la production des molécules soufrées clés de l’arôme et le second visant à limiter la formation des composés d’oxydation perturbateurs de l’arôme grâce à l’utilisation d’antioxydants naturels. Les recherches ont été conduites sur des mini-jambons cuits modèles. La thiamine a été identifiée comme précurseur majoritaire du 2-methyl-3-furanthiol, du 2-methyl-3-(methyldithio)furan, et du bis(2-methyl-3-furyl)disulfide dans les conditions de fabrication du jambon cuit et des extraits d’acérola, de canneberge, d’oignon et de thé ont été sélectionnés pour leurs propriétés antioxydantes. L’évaluation en parallèle de l’oxydation et de l’arôme a montré que ces quatre extraits utilisés en mélange permettaient, non seulement d’égaler les performances antioxydantes du nitrite, mais aussi de rehausser la note aromatique « jambon cuit » par rapport à la formulation non nitritée de référence. L’association de la thiamine et des extraits végétaux a finalement permis de réaliser des jambons non nitrités qui, en termes d’arôme et d’oxydation, se rapprochent fortement d’un jambon nitrité. Les formulations réalisées constituent donc une première piste satisfaisante pour répondre à la problématique de la suppression du nitrite dans le jambon cuit. La protection antimicrobienne des nouvelles formulations doit être validée et la restauration de la couleur rose du jambon demeure une problématique organoleptique. / Sodium nitrite is an essential ingredient in the cooked ham production process, yet its use is under challenge due to food safety concerns. Sodium nitrite is a multifunctional additive used for its ability to act on several fronts—from inhibiting oxidation and preventing microbial growth to giving desirable colour and aroma. This study focused on the aroma function under a wider objective to reduce nitrite use in cooked ham processing. Using several complementary methods with gas chromatography–olfactometry, we first identified 2- methyl-3-furanthiol, 2-methyl-3-(methyldithio)furan and bis(2-methyl-3-furyl)disulfide as the odour- active sulphur-compounds responsible for cooked ham flavour. It emerged that in the absence of nitrite—and therefore the absence of inhibited oxidation—the massive formation of an array of odour-active compounds produced by oxidative breakdown tended to disrupt the overall aroma of the final cooked ham. Next, in an effort to restore this aroma in the absence of nitrite, the study was organized into two strands, where the first strand aimed to promote the production of key aroma-active sulphur-compounds while the second strand aimed to minimize the formation of aroma-disruptive oxidation compounds by using natural antioxidants. This research was led on model cooked mini-hams. We identified thiamine as the major precursor of 2-methyl-3-furanthiol, 2-methyl-3-(methyldithio)furan and bis(2-methyl-3-furyl)disulfide under cooked ham production conditions, and we selected acerola, cranberry, onion and tea extracts as natural antioxidants. The coupled evaluations of oxidation and aroma showed that the formulated mixture of these four extracts not only equalled the antioxidant performances of added sodium nitrite but also lifted the “cooked ham” head note compared to the reference no-added-nitrite formulation. The association of thiamine and vegetal extracts ultimately made it possible to produce no-added-nitrite hams that, in terms of aroma and oxidation levels, proved almost identical to nitrite-added ham. The engineered formulations thus offer a good research track to suppress the sodium nitrite in cooked ham. The problem of how to restore the distinctive pink colour of cooked ham is an issue that remains to be resolved, and the ability of these new formulations to inhibit microbial growth needs to be validated.

Highly accurate analysis for the quantification of sulphur compounds and oxygenated volatile organic compounds are crucial for the adherence of the legislation in different environmental sectors. The sulphur compounds and oxygenated volatile organic compounds measurements are challenging, due to various factors such as molecules being adsorbed on the inner surfaces of cylinders. It is therefore important to produce accurate and reliable reference gas mixtures with mole fraction at ambient levels for the air quality monitoring and field of gas sensing in South Africa. The challenges in producing sulphur compounds and oxygenated volatile organic compounds reference gas mixtures are that the overall process from gravimetric preparation steps until the comparison analysis process and the stability of mixture in the gas cylinder, results in the large measurement uncertainties. In order to produce reference gas mixtures of the highest level, three important steps are followed: purity assessment of starting material, gravimetric preparation, and verification/validation of prepared gas mixtures. The purity analysis of high purity starting materials was determined using gas chromatography coupled with various detectors and Karl Fischer for determination of moisture content in high purity chemicals. The sulphur compounds and oxygenated volatile organic compounds to be developed in this study were hydrogen sulphide, sulphur dioxide, acetone, methanol, ethanol, isopropanol, and n-butanol. These components were produced following the International Organisation for Standardisation documents at mole fraction of 10 µmol/mol for sulphur compounds and 5 µmol/mol for oxygenated volatile organic compounds. The preparation of sulphur compounds reference gas mixtures was done with a static gravimetric method using a direct method where a target component was transferred directly into the cylinder. The preparation of oxygenated volatile organic compounds used an indirect method whereby a target liquid component from high purity chemicals was transferred into a cylinder using a gas-tight syringe.The comparison between the reference gas mixtures was validated using Non-Dispersive Ultra-Violet analysers (NDUV), gas chromatograph coupled with pulsed discharge helium ionisation detector (GC-PDHID, UV fluorescence analysers for sulphur compounds and gas chromatograph coupled with flame ionisation detector (GC-FID) for the oxygenated volatile organic compounds. A multi-point calibration method was used to analyse sulphur dioxide and hydrogen sulphide on the NDUV analyser, and the single-point calibration method was used for analysis on the gas chromatography and UV fluorescence where a sample mixture is analysed against a reference mixture with a similar mole fraction. The statistical data considered during analysis included calculation of the instrument drift and percentage relative standard deviation to check measurements repeatability, reliability, and measurement uncertainty. The gravimetric results of prepared sulphur compounds at 10 µmol/mol gave a percentage relative expanded uncertainty of 0.041 % REU for hydrogen sulphide, 0.12 % REU for sulphur dioxide. The gravimetric results of prepared oxygenated volatile organic compounds at 5 µmol/mol showed a percentage relative expanded uncertainty 0.068 to 0.35 % REU for isopropanol and ethanol respectively and less than 2.4 % REU for multi component of oxygenated volatile organic compounds. Finally, the primary standard gas mixtures of sulphur compounds and oxygenated volatile organic compounds were developed with the highest metrological measurement uncertainty level of (k=2). / Environmental Sciences / M. Sc. (Environmental Sciences)