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Faculty of Engineering and Built Environment

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    Desalination of a local oil refinery effluent to meet discharge limits
    (2021-12-01) Ezugbe, Elorm Obotey; Rathilal, Sudesh
    The Sustainable Development Goal Six (SDG 6) – “ensure availability and sustainable management of water and sanitation for all” places huge responsibilities on stakeholders (industry, domestic and agricultural) to prioritize water saving, water reuse and proper wastewater treatment to make potable water accessible everywhere in the world. With the industrial sector consuming nearly 20% of the fresh water available, there is a corresponding generation of large volumes of effluents. This has been projected to increase, as population is skyrocketing and more economies are becoming more industrialized to accommodate the needs of the ever-increasing population. Over the years, stringent effluent discharge limits have been imposed on the industrial sector to minimize the pollution of the receiving environments, especially the water bodies. In addition, wastewater treatment for reuse is being encouraged, which will ease the stress on freshwater resources. The oil refinery industry is noted for the generation of large volumes of effluents. These effluents are heavy laden with toxic and refractory materials as well as high concentrations of salts which pose huge environmental risks and detrimental ripple effects on humans and animals if these effluents are not properly treated before discharge. Unfortunately, the use of conventional treatment methods to treat downstream oil refinery effluent (ORE) has been unsuccessful in the removal of these materials, especially the salts. This research therefore, aimed at desalinating the effluent from the effluent treatment plant (ETP) of a local South African waste oil refinery to meet discharge limits. The ETP, even though successful in the removal of organics (COD, turbidity and colour), consistently records high levels of sulphates, chlorides and carbonates as a result of the source of their raw material and other in-house processes that take place during the treatment process. The study assessed and compared the feasibility of applying three membrane processes, viz forward osmosis (FO), reverse osmosis (RO) and hybrid FO-RO systems in desalinating the ORE. The FO and RO were first run as standalone processes, where models were generated and used to optimize the important factors using the Box-Benhken design (BBD) of response surface methodology (RSM). Based on the optimized conditions, the hybrid FORO was investigated. The basis of comparison was their permeation fluxes, salt rejection and flux recoverability after membrane cleaning. A total of 45 experimental runs were conducted which catered for pure water flux tests of virgin membranes, optimization studies and confirmatory runs. The factors of interest for FO were feed solution flow rate (FS-FR) (7.5 – 9.4 L/h), draw solution flow rate (DS-FR) (7.5 – 9.4 L/h) and draw solution concentration (DS-C) (20, 35 and 50 g/L NaCl). With RO, focus was placed on operating pressure (14 – 18 bar), feed concentration and operating time (4-6 h). The results showed an average permeation flux of 3.64 ± 0.13 L/m2 h, Clenrichment (reverse solute diffusion (RSD)) of 35.5 ± 5.15%, SO4 2- rejection of 100%, CO3 2- rejection of 94.59 ± 0.32 and flux recovery of 86.01 ± 2.66% for FO. For RO, the average permeation flux achieved was 2.29 ± 0.24 L/m2 h, Clrejection efficiency was 90.54 ± 0.81%, SO4 2- rejection efficiency was 95.1%, CO3 2- rejection efficiency was 97.3 ± 0.4 and flux recovery after membrane cleaning was 62.52 ± 2.62%. The FO-RO hybrid process proved unsuccessful due to constraints from the filtration unit. As an intervention to make the hybrid process work, NF was used as the recovery process. However, results show a low permeation flux of 0.69 ± 0.10 L/m2h on average. From the results obtained, it was concluded that RO presents the best desalination option for treating the ORE using low pressure of between 14 – 18 bar. This will require no post treatment and there will be no contamination of feed due to RSD
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    Application of kaolin-based synthesized zeolite membrane systems in water desalination
    (2021-12-01) Aliyu, Usman Mohammed; Isa, Yusuf Makarfi; Rathilal, Sudesh
    Accessibility to potable water worldwide is threatene, despite 71% of the earth’s surface being covered with water. However, 97% of the 71% is too saline for consumption. A usual way of treating salinity is by membrane desalination using reverse osmosis. The disadvantage of this approach is its high cost and short life span of the polymeric membrane used. Creating a new robust high-quality water treatment system using a ceramic membrane will address these challenges due to its robust mechanical properties. In this work, we synthesized different zeolites from South African kaolin under varying conditions such as crystallization time, ageing time and temperature and their effects on the properties of zeolites synthesized was investigated. Sample characterization confirmed the successful synthesis of ZSM-5 and zeolite A. In the synthesis procedure, metakaolin served as the alternative source of silica and alumina and was use to synthesize different types of zeolites under varying synthesis conditions. Synthesized samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and Brunauer–Emmett–Teller BET surface area. The properties of the synthesized ZSM-5 were influence by the synthesis parameters, typically, crystallization temperature, ageing time and crystallization time. Crystalline ZSM-5 zeolite produced at an ageing time of 24 hours, crystallization time of 48 hours and crystallization temperature of 180°C with Si/Al ratio of 43 and BET surface area of 282 m2 /g. After a 12-hour ageing period, Zeolite A produced at crystallization time of 20 hours, the crystallization temperature of 100°C, Si/Al ratio of 1.3 and BET surface area of 143.88 m2 /g. The findings indicate that aging influences the synthesis of zeolite A, as a relatively crystalline material formed at an ageing time of 12 hours, which continued to decrease as the ageing time was increased. We do not exclude the possibility of Ostwald ripening playing a role in this relationship. Subsequently, the efficiency of zeolite A and ZSM-5 zeolite in removing salt ions, Ca2+, K+ , Mg2+ , and Na+ from synthetic seawater was investigated at room temperature using a batch adsorption system. The effect of adsorbent dosage, agitation speed and contact time were consider. Dosages varied from 2.5 to 6.0 g/100 ml while the contact time varied from 30 to 180 minutes. The results obtained showed that a zeolite dosage of 6.0g/100 ml and agitation speed of 140 revolutions per minute (rpm) yielded a maximum removal efficiency of 89.7 % for Ca2+ and minimum removal efficiency of 1.8 % for Mg2+ at agitation rates of 30 and 120 minutes, respectively. Ion exchange of Na+ by Ca2+, K+ and Mg2+ in the zeolite framework was established. The preference of the overall ion-exchange selectivity of both zeolites A and ZSM-5 are in the order of Ca2+ > K+ > Na+ > Mg2+. Zeolite A showed higher removal efficiency compared to ZSM-5 zeolite. The results point out that the synthesized zeolite was able to desalinate the salt ions in synthetic seawater to a limit below the World Health Organization (WHO) recommended values. Consequently, zeolite synthesized from kaolin offers a cost-effective technology for the desalination of seawater. The desalination and material characterization results used in selecting a potential zeolite for use in reverse osmosis (RO). The material successfully deposited on etched alpha-alumina support to produce zeolite membrane by a hydrothermal technique using a modified in-situ method. Zeolite A and ZSM-5 membranes produced and applied in the RO unit for desalination. The RO membrane experimental results show potential in desalination of synthetic seawater. A machine-learning tool was use to predict the properties of the synthesized ZSM-5 as a function of the hydrothermal parameters. Finally, a techno-economic analysis of synthesizing zeolite using locally available kaolin at a capacity of 5 x 105 kg/yr. has shown that the plant is economically viable with rapid break-even and the payback period is less than 4 years.
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    Treatment and reuse of reactive dye effluent from textile industry using membrane technology
    (2014) Chollom, Martha Noro; Rathilal, Sudesh; Pillay, Visvanathan Lingamurti
    The textile industry consumes large volumes of water and in turn produces substantial quantities of polluted effluents. Approximately 30% of reactive dyes used during the textile processing remain unfixed on fibres and are responsible for the colouration in effluents. Various conventional methods are being used to treat textile effluent. However, the disadvantage of these methods is that total colour removal is not achieved and chemical by-products are introduced from the use of chemicals. The water quality produced therefore does not meet the requirement for textile reuse. Membrane based processes provide interesting possibilities of separating hydrolysed dye stuff and dyeing auxiliaries, thereby reducing colouration and COD content. They can be employed to treat reactive dye bath effluent to recover the salts and water for the purpose of reuse. This study aimed at integrating membrane processes into the reactive dye bath of a textile industry. The objectives were to determine the quality of permeate produced in terms of removal of organics, ascertain its reusability for dyeing, investigate the production rate in terms of permeate fluxes and finally to investigate the cleanability and flux recovery of the membranes. Three effluent samples were chosen for this study based on the dyeing recipe; Light shade, Medium shade and Dark shade. Ultrafiltration (UF) and Nanofiltration (NF) membrane processes were employed to treat the reactive dye bath effluents to recover the salts and water. Investigations were conducted firstly with UF as a pre-treatment to NF. Secondly, evaluations were carried out on the performance of two types of NF membranes (SR90 and NF90) in terms of permeate quality and fluxes for the investigated samples. The effect of cleaning on membrane performance was done. A reusability test was carried out on the permeate samples for dyeing. It was found that the use of UF as a pre-treatment yielded an increase in permeate of 5–25% of the NF fluxes and 90% in organics reduction for all treated samples, hence increasing the water recovery. High rejection of ˃90% by NF90 for COD, TOC and colour were obtained for all the treated samples. SR90 rejection was 80–90% for colour and ˃90% for COD and TOC. Salt recovery for NF90 was 60–90% and for SR90 was 40–50%. The reusability tests carried out showed that permeate recycled from NF90 can be used for any section in the textile industry including the most critical such as dyeing on light shades, while that from SR90 can be used for dyeing dark shades only. It was then concluded that membrane based processes can be integrated into the dye bath of the textile process for the purpose of reuse, thereby saving on the cost of chemicals (salts), reducing fresh water usage and reducing the extent of final effluent treatment.
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    Development of a flat sheet woven fabric membrane fermenter for xylanase production by Thermomyces lanuginosus
    (2015) Thorulsley, Venessa; Rathilal, Sudesh; Pillay, Visvanathan Lingamurti; Ramsuroop, Suresh
    Fermentation processes are vital for the production of numerous bioproducts. Fermentation being the mass culture of micro – organisms for the production of some desired product, is an extensive field, with immense prospects for study and improvement. Enzyme production is of significance as these proteins are biological catalysts, finding niches in numerous industries, xylanase for example is utilized in the pulp and paper, animal feed, biofuel and food production processes. During enzyme production, a critical step is biomass separation, whereby the valuable product, the enzyme, is removed from the broth or micro – biological culture before it is denatured. This is typically achieved via centrifugation. The aim of this study was to develop and evaluate a submerged membrane fermenter system with the specific outcome of increasing the rate of production of xylanase, from the thermophilic fungal species Thermomyces lanuginous DSM 5826. Preliminary shake flask experiments were performed to determine the optimal production conditions, followed by partial characterization of the enzyme. A bioreactor was then fabricated to include a flat sheet membrane module, with outlets for permeate and broth withdrawal and inlets for feed and sterile air input. Experiments were conducted to determine the optimal dilution rate for maximum volumetric productivity. Results from the shake flask experiments indicated that the best conditions for xylanase production, yielding xylanase activity of 5118.60 ± 42.76 U.mL-1 was using nutrient medium containing beechwood xylan (1.5 % w/v), yeast extract (1.5 % w/v), potassium dihydrogen phosphate (0.5 % w/v), adjusted to a pH of 6.5 and inoculated with 1.0 mL of spore solution, rotating in a shaking incubator set to 150 rpm at 50 °C. Apart from analysis of the effect of the carbon source on xylanase activity, coarse corn cobs were used in the shake flask experiments as a cost saving initiative. The pH optima was determined to be 6.5 while the temperature optima of the enzyme was 70 °C. SDS PAGE analysis revealed that the molecular weight of the enzyme was between 25 and 35 kDa and qualitative analysis via a zymogram revealed clear zones of hydrolysis on a xylan infused agarose gel. During short run membrane fermenter experiments the percentage increase in enzyme activity between the batch operation (610.58 ± 34.54 U.mL-1) and semi – continuous operation (981.73 ± 55.54 U.mL-1) with beechwood xylan nutrient replenishment was 60.78 %. The maximum volumetric productivity achieved with beechwood supplementation after 192 hours in semi – continuous operation (5.32 ± 0.30 U.mL-1.hr-1) was 2.1 times greater than that of batch operation (2.54 ± 0.14 U.mL-1.hr-1) which equates to an increase of 110.28 % in productivity measured at its peak. The increase in total activity between batch (610 576.92 U) and beechwood xylan medium supplemented semi – continuous mode (1 184 937.50 U) resulted in a 94.07 % increase. During long run experimental periods, the increase in production of xylanase between the batch (873.26 ± 61.78 U.mL-1) and the xylan medium membrane system (1522.41 ± 107.65 U.mL-1) was determined to be 74.34 % while an overall average increase in productivity between the batch and xylan fed membrane system was 43.25%. The total enzyme activity with in membrane mode with beechwood xylan nutrient medium feed was 160 % greater than the batch process offering a 2.6 – fold increase. Experiments where de – ionized water was alternated with beechwood xylan nutrient medium had no significant impact on the productivity or enzyme activity. The optimal dilution rate for maximum volumetric productivity as determined to be 0.0033 hr-1. The results are indicative of the potential viability of such a design, yielding the desired outcome of a membrane integrated system to significantly increase the production of enzymes during fermentation.