Theses and Dissertations (Chemical Engineering)

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    Flue gas desulphurization by spray dry scrubbing
    (Vaal University of Technology, 2022-03) Koech, Lawrence; Everson, R. C., Prof.; Hattingh, B. B., Prof.; Neomagus, H. W. J. P., Prof.; Rutto, H. L., Prof.
    Post combustion sulphur dioxide (SO2) emission is a major problem facing coal-based power plants. Increased awareness of the detrimental effects of SO2 on human health and the environment has prompted increased pressure to equip power plants with flue gas desulphurization (FGD) systems. FGD is a commercially proven technology for removal of SO2 from flue gas which is considered as a significant pollutant to the environment. Spray dry scrubbing (SDS) process represents a type of semi-dry FGD which is a low-cost retrofit SO2 control technology that could be used in already existing coal-fired power plants. This study explored the experimentation on the performance of a laboratory-scale spray dryer involving flue gas desulphurization (FGD). The experimentation involved test done to investigate the effects of spray characteristics i.e., inlet gas phase temperature, approach to saturation temperature, and calcium to sulphur ratio on SO2 removal efficiency using hydrated lime as a sorbent. Results indicated improved SO2 removal efficiency with increasing the stoichiometric ratio and decreasing the temperature and approach to saturation temperature. An absorption efficiency of SO2 beyond 90% was achieved at a stoichiometric ratio of 2.5. A high degree of conversion of calcium was realized at low stoichiometric ratios with a maximum utilization of 94% obtained at a stoichiometric ratio of 1.5. This study also investigated the interaction effects of independent variables on SO2 absorption using response surface methodology. By analyzing the influence of stoichiometric ratio, inlet gas phase temperature, slurry solid concentration and slurry pH, a predictive quadratic model was developed correlating the independent variables and SO2 removal efficiency. Although all independent variables had impact SO2 removal efficiency, stoichiometric ratio was found to have the largest influence. The recommended optimal conditions for SO2 absorption were inlet gas phase temperature of 140℃, stoichiometric ratio of 2, slurry solid concentration of 8% and slurry pH of 10 to achieve 90% SO2 removal efficiency. An investigation into performance of relevant spray dying FGD sorbents was carried by evaluating different sorbents namely: hydrated lime, limestone and trona. Results show that trona had better performance characteristics with the highest SO2 absorption efficiency when compared to hydrated lime and limestone under the same operating conditions. The analysis of the desulphurization product revealed that trona has better sorbent conversion and utilization in comparison with limestone and hydrated which contained high concentration of unreacted sorbent in the desulphurization product.
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    Application of nonwoven microfiltration membrane on activated sludge final effluent: improving wastewater quality for re-use
    (Vaal University of Technology, 2022-04) Masala, Murendeni Shonisani; Topkin, James; Tshilenge, J. Kabuba, Prof.
    Water scarcity is one of the biggest problems that South Africa is facing currently, as a results it limits economic and social development. The application of membrane technology in wastewater treatment for re-use is one of the alternatives to reduce the demand of water in domestic, agricultural and industrial sectors. The primary aim of this study was to improve effluent wastewater quality prior to disinfection for re-use. This was done by diverting biological nutrient removal (BNR) clarifier effluent to a pilot nonwoven membrane filtration unit. The physical barrier provided by this unit, together with the effect of aeration within this system, provided particulate, physicochemical, and microbial removal. Monitoring of water quality was attained from the BNR clarifier effluent, and the nonwoven membrane permeate. Water quality trends against the standards were analysed for compliance with a water use license (WUL), and the removal efficiency for the permeate was also determined. The Single Factor Pollution Index (Pi) was used to determine the extent of pollution in the BNR clarifier effluent and the permeate, while the Water Quality Index (WQI) was utilised to determine the suitability of water derived from the BNR clarifier effluent and the permeate for re-use. Water Use Licence standards were utilised to determine the Water Quality Index of the BNR clarifier effluent and the permeate. Results for the BNR clarifier effluent showed that the physicochemical water quality parameters comply with the limits however, electrical conductivity (EC) and microbial water quality Escherichia coli (E. coli) were exceeded. Permeate results indicated that physicochemical and microbial parameters were compliant with the limits of the WUL. E. coli reduction was the highest with a removal efficiency of 90%, followed by chemical oxygen demand (COD) at 25%, NH4N at 22%, NO3 at 12.6%, PO4 at 7.8%, suspended solids (SS) at 6.3%, and the lowest was EC at 5.2%. The Single Factor Pollution Index has revealed that the BNR clarifier effluent water quality is medium polluted and the permeate water quality is slightly polluted. The WQI results for the BNR clarifier effluent showed good water quality and the water can be re-used for domestic, irrigation, and industrial purposes, while permeate WQI results indicated excellent water quality and the water can be re-used for drinking, domestic, irrigation, and industrial purposes. Outstanding permeate water quality improvement was observed on E. coli counts improving from 4974.48 counts/L to 294.33 counts/L. The standard of E. coli according to the WUL at Waterval WCW is 500 counts/L. The results indicate that nonwoven membrane filtration can improve microbial contamination and decrease the demand of chlorine for disinfection of wastewater final effluent. The nonwoven membrane filtration can decrease the water scarcity gap in South Africa for direct water reclamation by improving effluent wastewater.
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    Application of neural network techniques to predict the heavy metals in acid mine drainage from South African mines
    (Vaal University of Technology, 2022-04) Maliehe, Andani Valentia; Osifo, P., Prof.; Matjie, H., Dr.; Tshilenge, John Kabuba, Prof.
    Acid mine drainage (AMD) refers to acidic water generated during mining activities and is characterised by a low pH, high salt content, and the presence of heavy metals. To treat water sources contaminated with AMD, sampling and laboratory analysis will have to be done for each water source to determine the concentrations of heavy metals. This process is time-consuming, high in cost and may involve human error or negligence. The application of neural network (NN) techniques to predict the heavy metals in AMD from South African mines has been presented. Four specific objectives were pursued in this dissertation. The first one was to identify AMD and analyse for heavy metals in the AMD. Heavy metals that were identified and found to be in high concentrations in the AMD sample from Sibanye Western Basin AMD Treatment Plant are Zn, Fe, Mn, Si, and Ni. The other objectives of the study were to determine the input, output, and hidden layers of the NN structure (application of NN); (2) to find the appropriate algorithm to train the NN, and to compare the NN results (outputs) with the measured concentrations of major heavy metals sampled (targets). The Backpropagation Neural Network (BPNN) model had three layers which included the input layer (pH, SO42−, and TDS), the hidden layer (five neurons) with a tangent sigmoid transfer function (tansig) and the output layer (Cu, Fe, Mn, and Zn) with linear transfer function (purelin). The predictions for heavy metals (Zn, Fe, Mn, Si, and Ni) using the NN method focusing on a BP forward pass (feed-forward backpropagation NN) with ten different algorithms were presented and compared with the measured data. The mean square error (MSE) value was calculated for ten algorithms and compared to identify the one that is most appropriate for the prediction process and the model by having the lowest value. It was determined that the Levenberg-Marquardt back-propagation (trainlm) algorithm resulted in the best fitting during training because it resulted in an MSE value of 0.00041, meaning the error was very low when this algorithm was used.
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    Production of adsorptive material from modified nanocrystals cellulose for industrial application
    (Vaal University of Technology, 2022-05) Banza, Musamba Jean Claude; Seodigeng, Tumisang, Prof.; Rutto, Hilary Limo, Prof.
    Water is the essence of life, yet it is progressively polluted by dyes, heavy metal ions, food additives, medicines, detergents, agrochemicals, and other toxins from industrial, municipal, and agricultural sources. Among the different wastewater treatment technologies, adsorption is a technique that, when used in conjunction with a welldesigned system, produces high-quality treated water at a reasonable cost. For water treatment, activated carbon is the most often employed adsorbent. Its manufacture, on the other hand, is energy demanding, costly, and creates greenhouse emissions. As a result, finding low-cost alternative adsorbents from industrial and agricultural waste and biomass has attracted a lot of interest. In this context, developing sustainable platforms for wastewater treatment using sustainable nanomaterials such as cellulose nanocrystals (CNCs) is a unique technique with a low carbon footprint. CNCs, which are made by hydrolyzing pulp fibers in sulfuric acid, are rod-like nanomaterials with a lot of remarkable qualities including high specific surface area, high specific strength, hydrophilicity, biodegradability, and surface functionalization. These characteristics, as well as their accessibility, make them suitable candidates for water treatment applications. However, because of their great colloidal stability and nano-dimensions, extracting these CNCs after usage in water treatment is difficult. To overcome this problem, including these CNCs into nanocomposite systems that can be readily separated after usage in batch and continuous water treatment processes is a great concept. Furthermore, pure CNCs have low selectivity towards a wide range of water pollutants, necessitating surface functionalization to provide this selectivity. As a result, this thesis investigates the extraction of CNCs from millet husk waste and waste papers, the development of CNC-incorporated nanocomposites and evaluation of their adsorption characteristics using batch and fixed bed column adsorption studies, and (ii) the evaluation of the selective adsorption characteristics of surface functionalized CNCs and their ability to tailor the nanocomposites' characteristics for use in water treatment applications. The response surface methodology, artificial neural network, and adaptive neuro-fuzzy inference systems were also applied to model the removal of heavy metal ions. The first part of the research ( cellulose nanocrystals extraction and optimization) The cellulose nanocrystals were extracted from millet husk residue waste using a homogenized acid hydrolysis method. The effects of the process variables homogenization speed (A), acid concentration (B), and acid to cellulose ratio (C) on the yield and swelling capacity were investigated and optimized using the Box Behnken design (BBD) method in response surface methodology. The numerical optimization analysis results showed that the maximum yield of CNCs and swelling capacity from cellulose was 93.12 % and 2.81 % obtained at homogenization speed, acid concentration, and acid to cellulose ratio of 7464.0 rpm, 63.40 wt %, and 18.83 wt %, respectively. ANOVA revealed that the most influential parameter in the model was homogenization speed for Yield and acid concentration for swelling capacity. The TGA revealed that cellulose had greater heat stability than CNCs. The functional groups of CNCs and cellulose were identical according to the FTIR data. When compared to cellulose, the SEM picture of CNCs is porous and shows narrow particle size with needle-like shape. The XRD pattern revealed an increase in CNC intensity. The second part of the research ( CNCs modification for selective removal) A novel type of recyclable adsorbents with outstanding adsorption capability was produced using CNCs with succinic anhydride and EDTA. and their adsorption properties were studied in detail utilizing batch adsorption experiments of Chromium (VI) in aqueous solution. The effects of several factors on Cr (VI) adsorption were examined, including contact duration, adsorbent dose, starting concentration, pH, and temperature. The cellulose nanocrystals treated with succinic anhydride and EDTA possessed a needle-like form, high porosity, and a narrow particle size distribution. The carboxylate transition of the carboxyl group of cellulose was verified by FTIR. XRD analysis of particles after modification revealed the presence of additional phases, which were attributed to succinic anhydride and EDTA modification. A spontaneous exothermic adsorption process was validated by the observed thermodynamic characteristics. The best model for describing adsorption kinetics and mechanism was a pseudo-second order kinetic and intra-particle diffusion model. The Langmuir adsorption isotherm was seen in equilibrium adsorption data, with a maximum adsorption capacity (qmax) of 387.25± 0.88 mgL-1. We showed that the removal effectiveness of Cr (VI) maintained at 220± 0.78 mg.g-1after 6 adsorption-desorption cycles, and that the CNC-ALG hydrogel beads are excellent adsorbents for the selective removal of Cr (VI) from wastewaters. The third part of the research ( modeling of removal of heavy metal ions using RSM, ANN and quantum mechanism studies ) The effects of contact time , pH, nanoparticle dose, and beginning Cd2+ concentration on Cd2+ removal were examined using the central composite design (CCD) technique. The performance and prediction capabilities of Response Surface Methodology (RSM) and Artificial Neural Network (ANN) modelling methodologies were explored, as well as their performance and prediction capacities of the response (adsorption capacity). The process was also described using the adsorption isotherm and kinetic models. Statistical data, on the other hand, revealed that the RSM-CCD model beat the ANN model technique. The optimum conditions were determined to be a pH of 5.73, a contact time of 310 minutes, an initial Cd2+ concentration of 323.04 mg/L, a sorbent dosage of 16.36 mg, and an adsorption capacity of 440.01 mg/g. The spontaneous adsorption process was well characterized by the Langmuir model, and chemisorption was the dominant regulator. The binding energy gaps HOMO-LUMO were used to find the preferred adsorption sites. The fourth part of research ( optimization of removal using ANN and ANFIS) An artificial neural network and an adaptive neuro-fuzzy inference system were utilized to predict the adsorption capability of mix hydrogels in the removal of nickel (II) from aqueous solution. Four operational variables were evaluated in the ANFIS model to determine their influence on the adsorption study, including starting Ni (II) concentration (mg/L), pH, contact time (min), and adsorbent dosage (mg/L) as inputs and removal percentage (percent) as the single output. In contrast, 70% of the data was employed to develop the ANN model, while 15% of the data was used in testing and validation. To train the network, feedforward propagation with the Levenberg-Marquardt algorithm was used. To optimise, design, and develop prediction models for Ni (II) adsorption using blend hydrogels, (ANN) and (ANFIS) models were employed for trials. The results demonstrate that the ANN and ANFIS models are viable prediction techniques for metal ion adsorption. The fourth part of research ( mechanistic modeling and optimization of removal using ANN, RSM and ANFIS) An artificial neural network, response surface methodology and an adaptive neuro-fuzzy inference system were utilized to predict the adsorption capability of modified cellulose nanocrystals and sodium alginate for the removal of Cr (VI) from aqueous solution. Four variables such as time, pH, concentration, and adsorbent dose were evaluated to determine their influence on the adsorption study. To examine the viability of the models, five statistical functions ( RMSE, ARE, SSE, MSE, and MPSD) were applied. absorption mechanism was described via four mechanistic models (Film diffusion, Weber and Morris, Bangham, and Dummwald-Wagner models. Further statistical indices supported ANFIS as the best prediction model for adsorption compared to ANN and RSM. Film diffusion was identified as the rate-limiting process via mechanistic modelling. The sixth part of research (continuous fixed-bed column study) The hydrogel's technical feasibility for adsorption of Cu2+, Ni2+, +Cd2+, and Zn2+ ions from the packed bed column's produced AMD was assessed. The hydrogel was considered to have a high potential for significant interactions with dangerous metal ions. This characteristic, together with the adsorbent's availability, low cost, and efficient regeneration of the spent adsorbent, distinguishes it from the many other adsorbents described in the literature by other researchers. With a bed height of 25 cm, an influent metal ion concentration of 10 mg/l, and a flow velocity of 10 ml/min, the bed performed better. As a consequence, the breakthrough curve for the packed bed experiment shows that the breakthrough points were approached sooner by increasing the flow rate and influent concentration, and later by increasing the bed height. The experimental results were satisfactorily described by the BDST, Yoon–Nelson, and Thomas models. The hydrogels had a net-work structure and more homogeneous porosity, according to the SEM, TGA, XRD, and FTIR results for CNCs. The hydrogels revealed varied degrees of opacity and heavy metal ions absorption capacity depending on the temperature of the analysis. Diffraction confirmed the existence of crystalline structures and the presence of carboxyl and amide groups.
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    Hybrid light photocatalysis of aromatic wastes in a fluidized bed reactor
    (Vaal University of Technology, 2022-08) Akach, John Willis Juma Pesa; Tshilenge, John Kabuba, Prof.; Aoyi, Ochieng, Prof.
    The use of solar photocatalysis for the treatment of aromatic chemicals like phenol in wastewater has attracted significant attention due to the low cost of sunlight. However, sunlight is unreliable since its intensity fluctuates during the day. This drawback can be addressed by supplementing sunlight with artificial UV lamps when the solar intensity reduces. In this work, such a hybrid solar/UV lamp reactor, internally illuminated by the UV lamp and externally by sunlight, was designed. Phenol was used as the model pollutant and the nanophase Aeroxide P25 TiO2 was employed as the photocatalyst and fluidized by compressed air. The catalyst and bubble distribution in the reactor was analysed using computational fluid dynamics (CFD) while the Monte Carlo (MC) method was used to model the light distribution and reaction kinetics. Finally, a lamp controller was designed to specify the required UV lamp output as a function of the solar intensity. The CFD simulation using ANSYS CFX 17 showed that a fairly homogeneous distribution of the catalyst was achieved in the reactor. Consequently, accurate simulations of the light distribution could be achieved without considering the hydrodynamics. The MC models revealed that bubbles did not significantly influence light absorption at the optimum catalyst loading. This showed that air was a good medium for fluidization as it could provide good mixing and oxygen electron acceptor without negatively affecting light absorption. The forward scattering behaviour of the P25 TiO2 and the increase in light attenuation with catalyst loading was confirmed in this work. The optimum catalyst loading in the different reactor configurations was 0.15 g/L (tubular solar), 0.2 g/L (annular solar), 0.4 g/L (annular UV lamp), and 0.4 g/L (hybrid light). This resulted in experimental reaction rates of 0.337 mgL-1min-1 (tubular solar), 0.584 mgL-1min-1 (annular UV lamp), and 0.93 mgL-1min-1 (hybrid light). An analysis of the local volumetric rate of energy absorption (LVREA) and reaction rate profiles along the radial coordinate showed a non-uniformity which worsened with an increase in catalyst loading. The reaction order with respect to the volumetric rate of energy absorption (VREA) indicated that solar illumination resulted in a higher electron-hole recombination as compared to UV illumination. This, combined with the higher intensity of the UV lamp, resulted in a higher reaction rate under UV light as compared to sunlight, demonstrating that the UV lamp could be used to supplement sunlight. For a typical sunny day, a lamp controller was designed that could adjust the UV lamp output as a function of the solar intensity to maintain the reaction rate at a reference level while ensuring less energy consumption than an ON/OFF lamp controller. This work demonstrated the feasibility of hybrid solar/UV lamp photocatalysis reactor which could maintain the advantages of solar photocatalysis while mitigating its drawbacks.
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    Electrocatalytic degradation of industrial wastewater using iron supported carbon-cloth electrode via Electro-Fenton oxidation process
    (Vaal University of Technology, 2021-02) Emeji, Ikenna Chibuzor; Ama, O. M., Dr.; Osifo, P. O., Prof.
    Human immunodeficiency virus (HIV) and acquired immune deficiency syndrome (AIDS) causes morbidity and mortality in infected patients. These epidemics are significantly reduced and treated globally with antiretroviral drugs (ARVDs). However, the eventual disposal of the ARVDs, either by excretion or otherwise, enables them to end up as emerging hazardous contaminants in our environment. Of all the available methods to remove ARVDs from our water bodies, electrochemical methods are reckoned to be one of the most effective. As a result, it is imperative to acknowledge the interactive behavior of these pharmaceuticals on the surface of the electrode. In this study, iron nano-particles were deposited on the carbon cloth electrode by electrodeposition using chronoamperometry techniques. The synthesized electrode was characterized using scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), and x-ray photoelectron spectroscopy (XPS) microanalysis. The electrochemical characterization of the material was also carried out using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrode's electrocatalytic activity toward the generation of hydrogen peroxide (H2O2) through a two-electron oxygen reduction reaction was assessed. Furtherance to this is the electrochemical degradation of nevirapine (NVP), lamivudine (LVD), and zidovudine (ZVD) in wastewater as a pharmaceutical model compound for organic pollutants in 50 mM K2SO4 electrolyte at a pH of 3. The SEM and EDX analysis showed the formation of iron nanoparticles within the matrix structure of the carbon cloth (CC) electrode. The XPS enlightened the presence of oxygen functional groups in the electrode's structure. EIS results are indicative that the modified electrode has a decreased charge transfer resistance (Rct)value as compared to the bare CC electrode. On the other hand, the CV result fosters good conductivity, enhanced current and large surface area of the modified electrode. More active and anchor sites were discovered on the iron-supported CC electrode which resulted in higher catalytic activity for the generation and accumulation of H2O2. The concentrations of “in-situ” generated H2O2 were found to be related to the current density supplied to the device after quantification. Although the accumulated H2O2 concentration appears to be low, it's possible that side reactions depleted the amount of H2O2 produced. As a result, the oxygen reduction reaction (ORR) through 2e- has a higher electrocatalytic activity with the improved iron assisted CC electrode than bare CC electrode. The electrochemical degradation studies conducted with the modified CC electrode by electro-Fenton process show a decrease in the initial ARVDs concentration (20 mg/L) as compared with the bare electrode. Their rate constants were 1.52 x 10-3 mol-1min-1 for ZVD, 1.20 x 10-3 mol-1min-1 for NVP and 1.18 x 10-3 mol-1min-1 for LVD. The obtained removal efficiencies indicate that the iron nanoparticle in the synthesised improves the degradation efficiency.
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    Biodiesel production and evaluation of heterogeneous catalyst using South African oil producing trees
    (Vaal University of Technology, 2014-01) Modiba, Edward Magoma; Osifo, Peter, Prof.; Rutto, Hillary, Dr.
    This study presents the use of sodium methoxide as a homogeneous catalyst and impregnated Perlite (potassium hydroxide/perlite) as heterogeneous catalyst for production of biodiesel using Baobab and Marula oil respectively. One factor at a time experimental design was used to study the effect of temperature, time, amount of catalyst and methanol to oil ratio on the transesterification of baobab oil using sodium methoxide as a catalyst. Response surface methodology was used to study the effect of temperature, time, amount of catalyst and methanol to oil ratio on the transesterification of marula oil using perlite as a catalyst. Biodiesel yield produced using sodium methoxide and baobab oil was 96% at 1 hr reaction time, 30 wt.% methanol to oil ratio, 1 gram of catalyst and 60°C reaction conditions. Biodiesel yield produced using perlite and marula oil was 91.38% at 3.55 hr reaction time, 29.86 wt.% methanol to oil ratio, 3.46 grams of catalyst and 70.41°C reaction conditions. Perlite catalyst was reusable for transesterification of marula oil while sodium methoxide was not reusable for transesterification of baobab oil. Baobab and Marula biodiesel fuel properties are comparable to American Society for Testing Materials standard (ASTM).
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    Synthesis of gelatin-cellulose hydrogel membrane for copper and cobalt removal from synthetic wastewater
    (Vaal University of Technology, 2021-04) Lukusa, Tresor Kabeya; Shoko, Lay, Dr.; Tshilenge, John Kabuba, Dr.
    Heavy metal ions are one of the most toxic materials in the environment. Adsorption is the most used process for the removal of heavy metals from wastewater. Much research has been conducted into processes to remove heavy metals using different adsorbents. Various adsorbents have been used to remove heavy metal ions from wastewater especially those that are harmful to mankind. Zeolite, clay, activated carbon and biopolymers are the most common adsorbents used. In this research, gelatin, and cellulose nanocrystals (CNCs) were used to synthesize a hydrogel membrane to remove Cu(II) and Co(II) metal ions from mining processes wastewater. The synthetic wastewater was prepared in the laboratory to conduct the experiments. Batch experiments were conducted to obtain the optimum conditions for the Cu(II) and Co(II) metal ions. The effect of parameters such as pH, ratio, contact time, and temperature were also determined. The optimum conditions obtained were 120 min contact time for both metal ions at the temperature of 30oC, pH 5 for copper and pH 7 for cobalt. The high removal of both metals ions was obtained using the ratio 3:1 (75% Gelatin and 25% CNCs) at the temperature of 303K. The maximum adsorption capacity of Cu(II) and Co(II) was 7.6923 mg/g and 10.988 mg/g, respectively. The high percentage removal of Cu(II) and Co(II) metal ions obtained was found to be 70.5% for Cu(II) at pH 5 and 74.5% for Co(II) at pH 7. The experimental data fit well to Pseudo-first-order kinetic and Freundlich isotherm models (KF= 1.89x103 mg/g for copper and 3.7x102 mg/g for cobalt) for both metal ions. The values of energy (E) from D-R model have shown that the adsorption of both metal ions was of physical nature (E<8kJ/mol) then confirmed by the thermodynamic results (ΔH°). The kinetic diffusion models have shown that the experimental data fit well with the film diffusion (R2= 0.977 and 0.989) for both metal ions at pH 5. Negative values of ΔG°obtained for both metal ions indicate that the adsorption process was spontaneous. The positive values of ΔH° obtained showed a physical adsorption process and also indicate that the adsorption process of both metal ions was endothermic. The positive values of ΔS° indicate an increase in randomness at the solid/solution interface during adsorption.
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    Development of sulfonated chitosan membranes modified with inorganic nanofillers and organic materials for fuel cell applications
    (Vaal University of Technology, 2021-07-06) Zungu, Nondumiso Petunia; Ofomaja, A., Prof.; Osifo, P. O., Prof.
    Fuel cell technology is a promising clean energy source compared to internal combustion engines and electricity generating plants which are associated with high emissions of greenhouse gases. The aim of this study was to modify chitosan into polymer electrolyte membranes suitable for use in PEMFC and DMFC fuel cells. Chitosan modification was done with 2-aminoethanesulfonic acid (2-AESA), dimethylformamide (DMF) and silica nanoparticles. The effect of the modification on the properties of the developed chitosan membranes was studied using FTIR, XRD, SEM-EDS and TGA. The performance of the membrane electrode assemblies was investigated. The formation of electrostatic interactions in the developed sulfonated chitosan membranes was confirmed via the Fourier transform infrared (FTIR) analysis, indicating a shift in the wavenumber of the N-H bonds from 1581 cm-1 on the chitosan spectrum to a lower wavenumber of 1532 cm-1 in the FTIR spectra of the membranes and by the new peak at the wavenumber of ~1260 cm-1 attributed to the asymmetric O=S=O stretching vibrations of the sulphate groups and sulfonic acid groups from the cross-linking sulphuric acid solution and 2-aminoethanesulfonic acid incorporated on the chitosan polymer chain during the modification. Notably, the FTIR spectra of the developed sulfonated chitosan membranes lacked the peak at the wavenumber of ~1153 cm-1 attributed to the stretching of C-O-C bonds of the polysaccharide ring of chitosan. A reaction mechanism was proposed in this study illustrating the possible conversion of the polysaccharide rings of chitosan into a poly (cyclohexene-oxide) thermoplastic rings in the developed membranes. The TGA/DTGA results of the developed sulfonated chitosan membranes showed three degradation stages. The initial weight loss occurred at temperatures ˂100 °C due to the evaporation of volatile components and water molecules inside the membranes. The second degradation phase of the membranes occurred at 208 ℃ with a loss in weight of >30% resulting from the decomposition of cross-linking networks. The third degradation stage was associated with the decomposition of the main polymer backbone of the membranes and occurred at 263°C for the chitosan membranes modified with 2-aminoethanesulfonic acid and at 266 °C for the chitosan membrane modified with silica nanofiller. The TGA/DTGA curves of Nafion 117 showed a small loss in weight of ~ 5% before a sharp decomposition that occurred between 346–505 °C. The XRD diffractograms of the developed sulfonated chitosan membranes showed amorphous phases, the crystal peaks of chitosan at 2theta of 10° and 20° were flattened on the membranes. The SEM images showed a homogenous surface morphology for the sulfonated chitosan membrane with a higher weight percentage of 2-aminoethanesulfonic acid (13,6 wt.%). The SEM images performed on the surface of the sulfonated chitosan membrane modified silica nanoparticles showed a slight agglomeration associated with the migration of the unbonded silica to the surface. The methanol permeability coefficient of the developed sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid was calculated to be 2.29x10-6 cm2/s. This value was close to the methanol permeability coefficient of 2.33x10-6 cm2/s associated with unfavourable depolarisation at the cathode in direct methanol fuel cells when using Nafion 117. The proton diffusion coefficient of Nafion 117 was calculated to be 1.64x10-5 cm2/s and that of the developed sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid was found to be 6.56x10-6 cm2/s, respectively. The fuel cell performance of the developed sulfonated chitosan membrane modified with 2AESA was investigated in a hydrogen fuel cell (PEMFC) supplied with H2 and O2 directly from the electrolyser. The sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid (13.6 wt.%) achieved an open-circuit voltage of ~0.9 V and a maximum power output of 64.7 mW/cm2 at a maximum current of 70 mA. The current produced by the developed chitosan membrane was applied into the load and was able to turn (power) the electric fan. The sulfonated chitosan membrane modified with silica nanoparticles (2 wt.%) yielded an open-circuit voltage of ~0.9 V and attained a maximum power output of 58 mW/cm2 at a maximum current output of 60 mA/cm2. The current generated by the membrane was also able to turn the electric fan. The Nafion 117 membrane was also investigated under similar conditions and obtained an open-circuit voltage of 0.6 V and a maximum power output of 130 mW/cm2 at the maximum current output of 308 mA. The current produced by Nafion 117 was supplied into the load and was able to turn the electric fan.
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    Modelling of in-situ real-time monitoring of catalysed biodiesel production from sunflower oil using fourier transform infrared
    (Vaal University of Technology, 2020-10) Mwenge, Pascal Kilunji; Rutto, H. L., Prof.; Seodigeng, T. G., Dr.
    The industrialisation of the twenty-first century and the worldwide population growth led to the high demand for energy. Fossil fuels are the leading contributor to the global energy, and subsequently, there is a high demand of fuels. The decrease of global fossil fuels and the environmental air pollution caused by these fuels are concerning. Therefore, eco-friendly and renewable fuel such as biodiesel is one the leading alternative. Chromatography and Spectroscopy are the most used analytical methods and proven reliable but are time-consuming, requires qualified personal, extensive samples preparation, costly and do not provide in-situ real-time monitoring. Fourier Transform Infrared (FTIR) has mainly been used for qualitative analysis of biodiesel, but not much work has been reported in real-time monitoring. This study focused on the modelling of in-situ real-time monitoring of the biodiesel production from sunflower oil using FTIR (Fourier Transform Infrared). The first part of the study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design (CCD). Biodiesel was produced by transesterification using Sodium Hydroxide as a homogeneous catalyst. A laboratory-scale reactor consisting of; flat bottom flask mounted with a reflux condenser, a hot plate as heating element equipped with temperature, timer and stirring rate regulator was used. Key parameters including, time, temperature and mixing rate, were kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65 % was obtained at a catalyst ratio of 0.5 wt% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R2 value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters range. The same set-up was used to produce waste margarine biodiesel using a homogeneous catalyst, potassium hydroxide (KOH). The effects of four reaction parameters were studied, these were: methanol to oil ratio (3:1 to 15:1), catalyst ratio (0.3 to 1.5 wt. %), temperature (30 to 70 oC), time (20 to 80 minutes). The highest yield of 91.13 % was obtained at 60°C reaction temperature, 9:1 methanol to oil molar ratio, 0.9 wt. % catalyst ratio and 60 minutes. The important biodiesel fuel properties were found to be within specifications of the American Standard Test Method specifications (ASTM). It was concluded that waste margarine can be used to produce biodiesel as a low-cost feedstock. The core of the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of the biodiesel production was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. Fourteen samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centring and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 values of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against the univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor transesterification of sunflower oil at industrial and lab scale. The model thus obtained, a batch reactor setup, EasyMax Mettler Toledodo reactor was used, the experiments were designed and monitored using iControl software. The results were recorded and quantified using iC IR software based on the biodiesel calibrated monitoring model built. The optimisation of the biodiesel was performed using three key parameters (methanol to oil ratio, catalyst ratio and temperature) while keeping time at 60 minutes and mixing rate at 150RPM. The highest yield of 97.85 % was obtained at 60 oC, 0.85 wt % catalyst ratio and 10.5 methanol to oil mole ratio. The analysis of variances of biodiesel production showed the values of 0.9847, 0.9674 and 0.8749, for R-squared, adjusted R-squared and predicted R-squared, respectively. A quadratic mathematical model was developed to predict the biodiesel conversion in the specified parameters ranges. Using the Arrhenius equation, activation energy (Ea) and frequency factor were found to be 41.279 kJ.mole-1 and 1.08 x10-4 M-1. s-1, respectively. The proposed kinetics model was a pseudo-first-order reaction. It was concluded that the model obtained can be used for industrial and laboratory-scale biodiesel production monitoring.
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    Biogas production from solid food waste and its use for electricity production
    (Vaal University of Technology, 2021-10-15) Khune, Selebogo Mervyn; Ochieng, Aoyi, Prof.; Otieno, Benton, Dr.; Osifo, Peter, Prof.
    An enormous amount of food waste (FW) is generated worldwide. Most of this waste is discarded in landfills, where it undergoes uncontrolled anaerobic digestion (AD) process, which emits excessive amounts of greenhouse gases, (methane and carbon dioxide), thereby contributing to global warming. A controlled AD of FW is key for organic waste management with a positive impact on the environment and economy. In South Africa (SA) there is little uptake of biogas technology for FW management due to little research on biogas potential at small to large scale. Furthermore, there is an over reliance on foreign data, which leads to misfit parameters to local raw materials; consequently, producing biogas of low quality and quantity with low degradation of waste. Biogas with poor quality reduces the efficiency of biogas conversion to energy and the low production rate makes the system less feasible. Considering the challenges faced with FW management and the little uptake of the AD technology in SA, this study aimed to treat FW through AD and convert the biogas produced to electricity. A complete-mix biogas pilot plant (VUT-1000C) was designed, constructed and commissioned. The materials used for constructing the pilot plant were sourced locally to prove the applicability of the AD technology in SA. The biodigester was operated at mesophilic temperature, 37 oC, aided by a solar system. A stand-alone 1 m3 plug-flow ambient biodigester (STH-1000A) was operated semi-continuously as well as a control. Cow dung (CD) was used to inoculate the biodigesters, which were then operated semi-continuously at their optimum organic loading rate (OLR). The STH-1000A digester was operated at 0.446 kgVS/m3/day OLR, according to the manufacturer’s specification, while for VUT-1000C, the OLR was determined. The highest biogas and methane yields obtained were 582 and 332 L/kgVS/m3, respectively, at the determined optimal OLR of 1.5 kgVS/m3/day for the VUT-1000C digester this was supported by the modified Gompertz model with an R2 value of 0.9836. VUT-1000C produced 1200 L/day while STH-1000A produced 150 L/day. VUT-1000C proved to be a more effective biodigester than STH-1000A owing to the digester design and operation at mesophilic conditions. The key design findings are higher reactor working volume and high digester temperature. From the 1000 L of biogas produced from VUT-1000C, 1.8 kW of electricity was generated, which is equivalent to powering 300 6W light bulbs for 1 hour. The energy balance of the pilot plant showed that only 10 percent of the energy output was required to operate the plant. These results show that SA has a 475 GWh energy potential based on the current FW figures. Furthermore, the study has shown that biogas technology is readily available for South Africans and that the designed biogas plant was very efficient in FW-to-energy conversion.
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    Thermomechanical and rheological properties of investment casting patterns
    (Vaal University of Technology, 2019-10-02) Tewo, Robert Kimutai; Focke, W., Prof.; Seodigeng, T., Dr.; Rutto, H. L., Prof.
    Investment casting process is the most suitable technique for producing high quality castings which are dimensionally accurate with excellent surface finish and complex in nature. Recently with the ever-changing manufacturing landscape, the process has been increasingly used to produce components for the medical, aerospace and sports industry. The present study looked at three investigative scenarios in the development of a pattern material for investment casting process: (i) the development of wax/ethyl vinyl acetate (EVA) and wax/linear low-density polyethylene (LLDPE) blends as the carrier vehicle materials for the development of pattern material for investment casting; (ii) the development of wax/EVA/polymethyl methacrylate (PMMA) based investment casting pattern and lastly (iii) the development of wax/LLDPE/PMMA based investment casting pattern material. The first part of the studies elucidates the effects in terms of the thermal, mechanical, surface and rheological properties when paraffin wax in blended with poly EVA and LLDPE. The developments involved the extrusion of seven formulations for EVA and also LLDPE using a twin-screw extrusion compounder. The paraffin wax weight percent investigated ranged from 33% to 87% thus encompassing both low and high wax loading ratios. The thermal properties of the developed binary blends were characterized via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The mechanical properties were characterized using three-point bending test. The thermo-mechanical and rheological properties were determined using thermomechanical analysis (TMA) and a rheometer respectively. A scanning electron microscope (SEM) was used to study the surface texture of the extruded blends. The thermal properties indicated that the thermal stability of paraffin wax is improved when it is blended with both EVA and LLDPE. DSC curves showed two endothermic melting peaks and two exothermic crystallisation peaks. In the case of wax/EVA blends, there was no distinct peak showing the independent melting of neat wax and EVA. The peak at a temperature of 50 – 72 °C corresponds to the melting of the wax/EVA blend. In the case of wax/LLDPE blends, the peak at 50 -66 °C corresponds to the melting of wax whereas the large peak at 112 - 125°C corresponds to the melting of the LLDPE. Wax/EVA and wax/LLDPE had improved mechanical properties as compared to that of neat wax. The rheological properties of both the EVA based and LLDPE based blends indicated that the viscosity of the blends increased as compared to that of neat wax. SEM confirmed that EVA alters the wax crystal habit at higher concentrations. In the case of wax/LLDPE blends, at 20-30 % wax content, a heterogeneous surface was observed, indicating the immiscibility of the paraffin wax within the LLDPE matrix. At a high wax content, there was agglomeration of wax. LLDPE allows amorphous structure of wax to disperse easily between the chains. The second part of the studies focussed on the wax/EVA filled with poly (methyl methacrylate) (PMMA) microbeads. TGA behaviour on the pyrolysis of wax/EVA/PMMA showed that the compounds volatilise readily with virtually no residue remaining above 500 °C. The DSC curves indicated that, the incorporation of PMMA reduced the crystallinity of wax/EVA blend. A distinct endothermic peak and another small peak was observed in all the formulations. The mechanical properties of wax/EVA/PMMA improved significantly. The methylene group present in both wax and EVA combined to form a blend with enhanced mechanical properties whereas the PMMA microbeads improved the needle penetration hardness. The melt viscosity of wax/EVA/PMMA increased as the EVA and/or the PMMA content is increased. The rheological experimental data fitted with the data predicted using the modified Krieger and Dougherty expression. The maximum attainable volume fraction of suspended PMMA particles was at max = 0.81. The SEM micrograph of wax/EVA/PMMA revealed a near perfect spherical nature for the filler particles in the wax/EVA polymer matrix. It further shows that the PMMA microbeads were weakly bonded and well distributed in the wax/EVA matrix. The third part of the studies focussed on the wax/LLDPE filled with Poly (methyl methacrylate) (PMMA) microbeads. The incorporation of LLDPE and PMMA into paraffin wax had a strong influence on the thermal properties, tensile properties, flow properties and its morphology. The TGA analysis showed that there was a slight observable decrease in the melting onset temperatures when the wax content was increased. From the DSC curves, the corresponding values of onset temperatures observed are between melting and crystallization temperature of neat paraffin wax and neat LLDPE. The short chains of the paraffin wax and the fragments formed by scission of wax chain have sufficient energy to escape from the matrix at lower temperatures. The slight decrease in peak temperatures associated with melting and crystallization could be attributed to the decrease in the average lamellar thickness of the blends. The tensile properties by three-point bending tests indicated an increase in the stress with an increase in the LLDPE content. This can be attributed to the formation of paraffin wax crystals in the amorphous phase of the blend which may influence the chain mobility. Since the paraffin wax used for this study had a low viscosity as compared to LLDPE, both LLDPE or PMMA had an influence on the viscosities of the blends. The data obtained from the experiments fitted with the data predicted obtained from the modified Krieger and Dougherty expression. The maximum attainable volume fraction of suspended PMMA particles was at max = 0.74. Similar observation with that of wax/EVA/PMMA was made in terms of the morphology of the wax/LLDPE/PMMA blends. The excellent thermal stabilities, the superior mechanical strength of wax/EVA/PMMA and wax/LLDPE/PMMA and the flow properties with relatively high EVA and also with high PMMA loadings, open new opportunities for EVA and LLDPE based pattern material for in investment casting process. It is worth pursuing further comprehensive studies since it offers a strong potential for realizing further technological improvement in the field of investment casting and rapid prototyping technologies.
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    Desulphurization of diesel fuel using carbon-based metal oxide nanocomposites
    (Vaal University of Technology, 2021-04) Cherubala, Rusumba Bienvenu; Rutho, L., Prof.; Tshilenge, J. K., Dr.
    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.
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    Optimization of ion exchange process on the removal of heavy metals from cooling tower water and regeneration of ion exchange resins.
    (Vaal University of Technology, 2020-06) Mbedzi, Robert Mbavhalelo; Rutto, H. L., Prof.
    In the present study, the removal of Ca2+ and Mg2+ from cooling tower water using Amberlite IR120 and Amberjet 1200 was studied by the application of one factor at a time method (OFAT) and response surface modelling (RSM). The effect of operational parameters such as contact time (min), pH, dosage (mL), concentration (mg/L) and temperature (K) were investigated using central composite design. The regeneration of the Amberlite IR120 and Amberjet were also studied. The purpose of the study was to apply OFAT and RSM to investigate and optimize the ion exchange operating parameters. Furthermore, the second-order empirical model that was developed, using the analysis of variance (ANOVA), presented a sufficient correlation to the ion exchange experimental data. The optimal ion exchange operating conditions for Amberlite IR120 and Amberjet 1200 were found to be: contact time was 120 min, dosage of 150mL, initial pH level of 2, concentration of 400mg/L and temperature of 343K. Regeneration of Amberlite IR120 and Amberjet 1200 using 0.5 M NaCl stripping solution initially showed an increase in % Ca2+ and Mg2+ removal, then a decrease in subsequent cycles. The correlation coefficients (R2) of Langmuir, Freudlich and Tempkin isotherms were found to range from 0.92 to 1 and this suggest that experimental data best described the models. However correlation coefficients (R2) for Dubinin–Radushkevich (D-R) model were found to range between 0.5 to 0.8 and this means that experimental data does not fit the model. Thermodynamic functions such as entropy (Δ𝑆𝑜), enthalpy (Δ𝐻𝑜) and change of free energy (Δ𝐺𝑜) were obtained from the gradient and intercepts of straight line graphs. The positive values of ΔG° were found meaning that the adsorption is not spontaneous and positive values of ΔH° were found meaning the endothermic type of adsorption which indicate the chances of physical adsorption.The correlation coefficient (R2) values of pseudo-first-order, pseudo-second-order and intraparticle models were found to range from 0.89 to 1 on both metals as shown in table 4.4. This observation clearly indicates that pseudo-first-order, pseudo-second-order and intraparticle diffusion models best describe the experimental data in the removal Ca2+ and Mg2+ from cooling tower water.
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    Activation of the carbonaceous material from the pyrolysis of waste tires for wastewater treatment.
    (Vaal University of Technology, 2017-07) Malise, Lucky; Seodigeng, T., Dr.; Rutto, H. L., Dr.
    The generation of waste tires is one of the most serious environmental problems in the modern world due to the increased use of auto mobiles all over the world. Currently there is a problem with the disposal of waste tires generated since there are strict regulations concerning their disposal through landfill sites. Therefore, there is a need to find ways of disposing these waste tires which pose serious health and environmental problem. The pyrolysis of the waste tires has been recognised as the most promising method to dispose the waste tires because it can reduce the weight of the waste tires to 10% of its original weight and produce products such as pyrolysis oil, pyrolysis char, and pyrolysis char. These products can be further processed to produce value added products. The char produced from the pyrolysis of waste tires can be further activated to produce activated carbon. This study is based on the chemical activation of waste tire pyrolysis char to produce activated carbon for the removal of lead ions from aqueous solution. This was done by impregnating the waste tire pyrolysis char with Potassium hydroxide and activating it inside a tube furnace under inert conditions to produce waste tire activated carbon. Adsorbent characterisation techniques (SEM, FTIR, TGA, XRF, XRD, BET, and Proximate analysis) were performed on the waste tire pyrolysis char and the activated carbon produced to make a comparison between the two samples. The results showed that the waste tire activated carbon produced has better physical and chemical properties compared to the raw waste tire pyrolysis char. Adsorption results revealed that waste tire activated carbon achieves higher removal percentages of lead ions from aqueous solution compared to waste tire pyrolysis char. The results also showed the effect of various process variables on the adsorption process. Adsorption isotherms, kinetics, and thermodynamics were also studied. The adsorption of lead ions agreed with the Freundlich isotherm model for both the waste tire pyrolysis char and waste tire activated carbon. In terms of adsorption kinetics, the experimental data provided best fits for the pseudo-first order kinetic model for both the waste tire pyrolysis char and the waste tire activated carbon. The adsorption thermodynamics study revealed that the process is an exothermic process and spontaneous in nature. Response surface methodology was used to determine the combined effect of process variables on the adsorption of lead ions onto waste tire activated carbon and to optimise the process using numerical optimisation. The optimum conditions were found to be adsorbent dosage = 1g/100ml, pH = 7, contact time = 115.2 min, initial meta concentration = 100 mg/l, and temperature = 25°C to achieve a maximum adsorption capacity of 93.176 mg/l.
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    Integrated anaerobic digestion and UV photocatalytic treatment of industrial wastewater in fluidized bed reactors
    (Vaal University of Technology, 2017-03-28) Apollo, Seth Otieno; Onyango, Maurice S., Prof.; Aoyi, Ochieng, Prof.
    Anaerobic digestion (AD) is usually applied in the treatment of distillery effluent due to the fact that it is effective in chemical oxygen demand (COD) reduction and bioenergy recovery. However, due to the presence of biorecalcitrant melanoidins present in distillery effluent, AD is ineffective in colour reduction. For this reason, ultraviolet (UV) photodegradation, which is effective in melanoidins’ degradation, can be integrated with AD to achieve high efficiency in colour and COD reduction. However, the UV process is energy intensive, majorly due to the electricity requirement of the UV lamp. In contrast, the AD process has high potential of renewable energy production in the form of biomethane, which can be transformed into electrical energy and applied to supplement the energy requirement of the UV process. The aim of this study was to evaluate the efficiency of a combined AD-UV system in colour and COD reduction for the treatment of distillery effluent in fluidised bed reactors. The potential of the application of the bioenergy produced by the AD process to supplement the energy intensive UV process was evaluated and modelled using response surface methodology. In the first place, the optimal hydrodynamic conditions of the fluidised bed reactors were determined using optical attenuation technique. The best homogeneity in the bioreactor, in which zeolite was used as microbial support, was found to be at a superficial liquid velocity of 0.6 cm/s while the best catalyst and gas hold up in the photoreactor were found to be 0.077 and 0.003, respectively. At these conditions, it was found that the initial biological step removed about 90% of COD and only about 50% of the colour while photodegradation post-treatment removed 98% of the remaining colour. Kinetic analysis of the bioreactor showed that ~ 9% of the feed total organic carbon (TOC) was non-biodegradable and this was attributed to the biorecalcitrant melanoidins. Photodegradation post-treatment mineralized the biorecalcitrant melanoidins via a reductive pathway as was indicated by the formation of NH4+ in large quantity compared to NO3-. Kinetic analysis further showed that the rate of substrate utilization in the bioreactor increased with an increase in organic loading rate and it was inversely proportional to the rate of photodegradation post-treatment. Modeling using response surface methodology (RSM) was applied to predict the effects of the operating parameters of the initial AD step on the performance of the photodegradation post-treatment process and the energy efficiency. Energy analysis of the integrated system showed that the AD process could produce 59 kWh/m3 of electricity which could supplement the electricity demand of the UV lamp by 30% leading to operation cost reduction of about USD 4.8/m3. This led to a presumed carbon dioxide emission reduction (CER) of 28.8 kg CO2e/m3.
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    Modelling of Petroleum Wastewater Photodegradation in a Fluidized Bed Reactor
    (Vaal University of Technology, 2018-04) Nyembe, N.; Lerotholi, M.; Aoyi, Ochieng, Prof.
    Petroleum wastewater is highly contaminated with toxic organic pollutants that are harmful to the environment. The heterogeneous photocatalytic oxidation (HPO) process has shown the ability to remove these pollutants through the application of a fluidized bed reactor (FBR). The purpose of the study was to apply response surface modelling (RSM) and computational fluid dynamics (CFD) to optimize the operating conditions for the photodegradation process in an FBR. This was done by investigating the hydrodynamics, photodegradation efficiency and reaction kinetics; that gave a holistic view on the performance of the FBR. The hydrodynamic study focused on modelling the axial liquid velocity, gas hold-up and turbulence quantities due to their substantial impact on the design and performance of the FBR. This was done by implementing the Eulerian-Eulerian approach which solves the continuity and momentum equations for each phase. In addition, the standard k-ε turbulence model was used to capture the turbulent characteristics in the liquid phase. A numerical optimization technique (desirability) was used to determine the optimal simulation setting methods; that were found to be a fine grid size (500 000 cells), 2nd Order Upwind discretization scheme and a small time step size (0.001) and gave the best desirability (0.985). The axial liquid velocity was maximal towards the centre of the reactor and decreased towards the wall. The same trend was seen with the local gas hold-up, where it was high towards the centre and low near the wall region. This was an indication that the bubbles tended to gather towards the central region as they move up. Furthermore, the bubbles had a spherical–like shape due to the low superficial gas velocity and operating within the homogeneous regime. The turbulent kinetic energy increased at distances away from the distributor region, due to the bubbles accelerating, and it balanced well with the energy introduced by the bubbles. Central composite design (CCD), which is a type of response surface modelling technique, was used to investigate and optimize the photodegradation operating parameters. The maximal degradation efficiency in the current study was found to be 65.9%, which was relatively low when compared to literature (80.84%). This was attributed to the increase in the catalyst particle size from nanometer to micrometer. Furthermore, the second-order empirical model that was developed, using the analysis of variance (ANOVA), presented a sufficient correlation to the photodegradation experimental data. The optimal photodegradation operating conditions were found to be: superficial gas velocity of 17.32 mm/s, composite catalyst loading of 1.0 g/L, initial pH level of 3.5 and reaction time being 210 min. Using the Langmuir-Hinshelwood model, it was found that the photocatalytic degradation of petroleum wastewater follows pseudo first-order reaction kinetics. Since the photocatalytic degradation mechanism of phenol follows three stages whereby the second stage is the photocatalytic degradation on the surface of the catalyst to form by-products. This is the rate dominant stage and follows the pseudo firstorder reaction kinetics.
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    The adsorption of Cu(II) ions by polyaniline grafted chitosan beads.
    (Vaal University of Technology, 2013-11-06) Igberase, Ephraim; Ofomaja, A., Dr; Osifo, P.O., Dr
    This work investigates the possible use of chitosan beads and polyaniline grafted chitosan beads (PGCB) for the adsorption of copper ions from copper contaminated water. For this purpose chitosan flakes were converted to chitosan beads. However, a variable from a number of reaction variables (aniline concentration, chitosan concentration, temperature, acid concentration, reaction time and initiator concentration) was varied while others was kept constant, in an attempt to determine the best conditions for grafting of polyaniline onto chitosan beads. Percentage (%) grafting and % efficiency were key parameters used to determine such conditions. The chitosan beads and PGCB were characterized using physical techniques such as Fourier transformed infra red (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). The beads were used as an adsorbent for copper ions removal. The effect of pH on the removal rate of copper (II) by PGCB was investigated on by varying the pH values from pH 3 to 8 at an initial concentration of 40 mg/l. The effect of contact time, initial concentration and temperature was also investigated. The Langmuir and Freundlich model were used to describe adsorption isotherms for chitosan beads and PGCB, with correlation coefficient (R2) as the determining factor of best fit model. The thermodynamics of adsorption of copper (II) onto PGCB was described by parameters such as standard Gibb’s free energy change (ΔGo), standard enthalpy change (ΔHo), and standard entropy change (ΔSo) while the pseudo first-order and pseudo second-order kinetic model was used to describe kinetic data for the PGCB, with R2 and chi- square test (  2) as the determinant factor of best fit model. From the desorption studies, the effect of eluants (HCl and HNO3) and contact time on percentage desorption of PGCB loaded copper (II) ion was investigated upon. In determining the reusability of the PGCB loaded copper (II) ion, three cycles of adsorption/desorption studies was carried out. The results obtained from determining the best conditions for grafting polyaniline onto chitosan beads revealed the following grafting conditions; [Aniline] 0.1 g/l, [temperature] 35oC, [chitosan] 0.45 g/l, [HCl] 0.4 g/l, [(NH4)2S2O8] 0.35 g/l, and [time] 1 h. These conditions were applied in the grafting of polyaniline onto chitosan beads. FTIR analysis showed increase intensity in the grafted beads which provided evidence of grafting, XRD measurement showed a decrease in crystallinity in the PGCB as against the partial crystalline nature of chitosan. In SEM analysis, evidence of grafting was revealed by the closed gap between the polysaccharide particles in the PGCB. From the investigation carried out on the effect of pH on the percentage removal of Cu(II) ions by PGCB, the optimal pH value was found to be pH 5 with a percentage removal of 100% and this value was used for all adsorption experiment. Also from the investigation performed on the effect of contact time and initial concentration, it was observed that there was a sharp increase in the amount of Cu(II) ions adsorbed by PGCB up until contact time of 30 min and thereafter, it increases gradually. From the experiment carried out on the effect of temperature on adsorption capacity, there was an increase in adsorption capacity with increase in temperature. Moreover, at temperatures of 25oC, 35 oC and 45oC the Langmuir model gave the best fit for the chitosan beads having R2 values that are equal and greater than 0.942 in contrast to Freundlich having R2 values that is equal and greater than 0.932. The maximum adsorption capacity (Qm) from Langmuir model at these temperatures were 30.3 mg/g, 47.6 mg/g and 52.6 mg/g respectively. Also, the Langmuir model gave the best fit for the PGCB having R2 values that are equal and greater than 0.956 in contrast to Freundlich model with R2 values that is equal and greater than 0.935. The Qm from Langmuir model at these temperatures were 80.3 mg/g, 90.9 mg/g and 100 mg/g respectively. The values of Qm for PGCB appears to be significantly higher when compared to that of chitosan beads and this makes PGCB a better adsorbent than chitosan beads. From the thermodynamic studies carried out on PGCB, the values of ΔGo were negative and this denotes that the adsorption of copper ions onto PGCB is favorable and spontaneous, the positive value of ΔHo shows the adsorption process is endothermic and the positive value of ΔSo illustrate increased randomness at the solid-liquid interface during the adsorption process. Also, from the kinetic studies carried out on the PGCB, the pseudo second-order kinetic model best described the kinetic data having R2 values that are equal and greater than 0.994 in contrast to the pseudo first-order kinetic model with R2 values that is equal and greater than 0.913. The  2 values for the pseudo first-order and pseudo second-order kinetic model were similar; however, there was a large difference for qe between the calculated (qeCal) values of the first-order kinetic model and experimental (qeExp) values. In the case of the pseudo second-order model, the calculated qe values agree very well with the experimental data. Desorption of the metal ions from PGCB was efficient. 0.5 M HCl was successfully used in desorbing the beads loaded with copper ions and a percentage desorption of 97.1% was achieved at contact time of 180 min. PGCB were successfully re-used for adsorption/desorption studies were a Qm of 83.3 mg/g, 83.3 mg/g and 76.9 mg/g was achieved in the first, second and third cycle respectively.
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    Desulfurization of waste tire pyrolytic oil (TPO) using adsorption and oxidation techniques
    (2018-01) Mello, Moshe; Seodigeng, T; Rutto, H. L.
    The presence of tires in open fields, households and landfills is a great threat to the wellbeing of the ecosystem around them. Tire creates an ideal breeding ground for disease carrying vermins and their possible ignition threatens the surrounding air quality due to the harmful gases produced during combustion. Pyrolysis of tires produces four valuable products namely; char, steel, tire pyrolytic oil (TPO) and noncondensable gases. TPO has been reported to have similar properties to commercial diesel fuel. The biggest challenge faced by TPO to be used directly in combustion engines is the available sulfur content of about 1.0% wt. Considering the stringent regulations globally for allowable sulfur content in liquid fuels, TPO therefore, requires deep desulfurization before commercialization. In this study, different desulfurization techniques were applied to reduce the sulfur content in TPO. A novel study on combination of adsorptive and air-assisted oxidative desulfurization (AAOD) was developed for desulfurization of TPO. Different carbon materials were employed as catalyst and/or adsorbent for the AAOD system. The effect of operating conditions; catalyst/adsorbent dosage, H2O2/HCOOH ratio, reaction time, temperature and air flowrate were studied. Oxidation equilibrium was reached at 80 °C for both commercial activated carbon (CAC) and activated tire char (ATC) at a reaction time of 50 min. With a total oil recovery of more than 90% and the initial sulfur content of 7767.7 ppmw, the presence of air at a flow rate of 60 l/hr increased oxidation from 59.2% to 64.2% and 47.4% to 53% for CAC and ATC, respectively. The use π-complexation sorbent was also applied to study the selectivity of such sorbents to organosulfur compounds (OSC) found in liquid fuels. The π-complexationbased adsorbent was obtained by ion exchanging Y-zeolite with Cu+ cation using liquid phase ion exchange (LPIE). Batch adsorption experiments were carried out in borosilicate beakers filled with modified Cu(I)-Y zeolite for both TPO and synthesized model fuels. For model fuels (MF), the selectivity for adsorption of sulfur compounds followed the order dibenzothiophene (DBT)> benzothiophene (BT)> Thiophene.
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    Corrosion behaviour of ferrous and non-ferrous alloys exposed to sulphate - reducing bacteria in industrial heat exchangers
    (Vaal University of Technology, 2018) Prithiraj, Alicia; Osifo, Prof. P. O.; Otunniyi, Prof. I. O.
    Corrosion responses of some carbon steels, stainless steel and copper alloys in the presence of a culture of bacteria (referred to as SRB-Sulphate-reducing bacteria) found in industrial heat exchangers, was studied to recommend best alloys under this service condition, with techno-economic consideration. Water from cooling towers in three plants in a petrochemical processing complex were analysed for SRB presence. Two of the water samples showed positive indication of SRB presence. The mixed cultures obtained from plant one were grown in prepared media and incubated at 35 °C for 18 days. Potentiodynamic polarisation studies in anaerobic conditions were done on the selected alloys in aqueous media with and without the grown SRB. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were then used to study the corrosion morphology and corrosion products formation. The voltamograms show higher icorr for alloys under the SRB compared to the control media, indicating the SRB indeed increased the corrosion rates. The surface analysis showed pitting on steel alloy ASTM A106-B. Localised attack to the grain boundaries on a selective area, was seen on ASTM A516-70 dislodging the grains, and intergranular corrosion was seen throughout the exposed area of ASTM A179. Copper alloys showed pitting on ASTM B111 grade C71500 (70-30), and denickelification on ASTM B111 grade C70600 (90-10), and is a good alternative material for use apart from carbon steel alloys, recording a low corrosion rate of 0.05 mm/year. The EDS analysis supported the findings showing higher weight percent of iron and sulphur on surface of the alloys after exposure to the SRB media. This implies that the presence of the sulphur ion indeed increased the corrosion rate. ASTM A516-70 carbon steel was chosen as a suitable alternative material to the stainless steel in this environment. The Tafel plot recorded a corrosion rate of 1.08 mm/year for ASTM A516-70 when exposed to SRB media.