Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2018. / The rate of waste electrical and electronic equipment (WEEE) is growing at an alarming rate, especially in countries where markets are saturated with huge quantities of new electronic goods. Printed circuit boards (PCBs) are a substantial portion of the value contained in waste from WEEE although they are only 6% of the total weight. It is reported that WEEE is currently the fastest growing waste stream in South Africa as the general population’s access to electronic goods in the last decade has increased, especially access to mobile phones. PCBs are found in any piece of electrical or electronic equipment and consist of various metals including precious metals such as gold (Au), silver (Ag) and palladium (Pd). It is reported that gold has the highest economic incentive at 15,200 $ per ton of PCBs. The rapid introduction of new and advanced technology into mobile phones has caused mobile phones to have a relatively short life span, 1 to 2 years to be exact. Mobile phones printed circuit boards (MPPCBs) have more Au content compared to computer circuit boards. They contain 350 g/ton Au whereas computer (PC) PCBs contains 250 g/ton. This research project will recover gold from waste mobile phones PCBs pregnant ammonia thiosulphate leach solution using copper cementation. The cementation process is preferred to all the other technologies of metals extraction from solution due to ultrahigh purity metals that can be obtained and to the less consumption of materials and energy. Electronic parts on the PCBs were manually removed using pliers and screwdrivers. PCBs were then cut to smaller pieces of about 2 x 2 m. The pieces were crushed and milled respectively. Some of the particles were recycled back to the crusher to get finer particles. The particles were separated to particles of sizes between 0 and 1350 μm using a shaker. The comminuted fractions of the PCBs were then used in the leaching step. Batch cementation experiments were performed by bubbling N2 in glass reaction vessel with a working volume of 0.5 L. The reactor was connected to a circulating water bath for temperature control. The recovery percentage of gold at various temperatures, agitation speeds and different amounts of copper powder used, was determined while pH was monitored. The temperature was varied at 30 °C, 40 °C, and 50 °C and the agitation speeds at 300 RPM and 900 RPM. Copper powder was added at 0.5 g/L, 1 g/L, and 1.5 g/L. Gold concentrations were measured by atomic adsorption spectrophotometer (AAS). Scanning electron microscope (SEM) and Energy-dispersive x-ray spectrometry (EDS) analyses of the copper powder after cementation (precipitates) were used to determine the surface morphology and to evaluate the quantitative aspect of the precipitate. It was found that the recovery of gold from ammonia thiosulphate leach solution was greatly affected by agitation speed. At an agitation speed of 900 rpm, 40 °C and 0.5 g of Copper powder, 96% of the gold was recovered from the leach solution. The cementation rate increased as temperature was elevated from 30 to 40 °C, but slightly decreased as the temperature reached 50 °C. The change in experimental conditions affected the gold concentration on the precipitate recovered. This study will provide a possible solution to the WEEE problem and more specifically mobile cell phones, in South Africa.

Different types of biomass samples including fungi and algae were treated for their gold and cobalt uptake capacity. The performance of activated carbon and ion-exchange resins were compared with the metal uptake capacity of the biosorbents. Sargassum natans, a brown seaweed, exhibited a high gold uptake capacity outperforming the ion-exchange resin and equalling activated carbon. Algal biomass of Ascophyllum nodosum proved to be a very potent biosorbent for cobalt. While the temperature, agitation and biomass particle size did not affect the metal uptake process, the effect of pH was significant for both gold and cobalt uptakes. The optimum pH for gold uptake was 2.5 and for cobalt, was 4-5. The kinetics of cobalt biosorption was relatively rapid (5 min) at the initial concentration of the metal in solution, 100 mg/L. The biosorptive uptake of gold required 2 h to reach equilibrium when the initial concentration of gold was 100 mg/L. None of the tested cations, such as K$ sp+$, Ca$ sp{2+}$, Fe$ sp{2+}$, Cr$ sp{3+}$, UO$ sbsp{2}{2+}$, Ni$ sp{2+}$, Zn$ sp{2+}$, Ag$ sp+$, affected the gold uptake capacity of S. natans biomass under the optimum conditions. Anions, such as NO$ sbsp{3}{-}$, SO$ sbsp{4}{2-}$, CO$ sbsp{3}{2-}$, PO$ sbsp{4}{3-}$, and Pb$ sp{2+}$ suppressed the gold uptake somewhat. Under the optimum process conditions cations, except K$ sp+$ and Fe$ sp{2+}$, and anions, NO$ sbsp{3}{-}$ in particular, exhibited a pronounced negative effect on the cobalt uptake by A. nodosum biomass. / Sequestered gold was eluted with a mixture of thiourea and ferric ammonium sulphate solution. Approximately 98% of sequestered gold was eluted with 17 h in a batch contacting system at the optimum solids (biomass)-to-liquid ratio of 5 and pH of 5. At increased temperatures, the gold elution rate increased only slightly. Efficient desorption of cobalt was achieved using CaCl$ sb2$/HCL solution at pH 3. Cobalt elution time was quite short. Temperature affected neither desorption rate nor the equilibrium. The optimum solid-to-liquid ratio was 12 for desorption of cobalt from A. nodosum biomass. / The gold taken up by the biosorbent was deposited in its elemental form. / Available mathematical models, including the REDEQL2 chemical equilibrium model, were tested for theoretical predictions of co-ion competition in attempt to better understand the biosorption mechanism. (Abstract shortened with permission of author.)

Waste water from the mining industry is generally extremely complex and contains numerous species which influence the adsorption of the metals to any biomass. A variety of factors need to be addressed before treatment is considered viable. It is also beneficial to establish the binding characteristics of the metal of interest to maximise its interaction with the biomass to be utilised. Azalia filiculaides was investigated in the adsorption of gold(III), lead(II), iron(ID), copper(II) and platinum (IV). In batch studies, the optimum biomass and initial gold(III) concentrations were found to be 5 gIL and 8 mgIL respectively. The adsorption of gold(ID) is principally pH-dependent with optimal removal at pH 2. Lead(II), iron(III) and copper(II) did not compete with gold(III) adsorption under equimolar and simulated effluent conditions. Halides, with increasing affinity for gold (chloride < bromide < iodide), can affect gold uptake with the soft base, iodide, exhibiting the most inhibition (25%) and the hard base, chloride, O%. Mercaptoethanol (soft base) showed no interference in gold(III) adsorption while the presence of sulphate (hard base) and sulphite (borderline base) showed that concentrations in excess of 1 0 mM may adversely affect gold(ill) uptake, most likely due to competition for cationic sites on the biomass. Column studies, better suited to high volume treatment, indicated that a flow-rate of 5 mL/min and an initial gold(ill) concentration of 5 mgIL was optimal. Competitive effects between lead, iron, copper and gold again showed little or no interference. The halides, chloride, bromide and iodide, affect gold(ill) uptake similarly to the batch studies, while the bases mercaptoethanol and sulphate minimally affect gold(III) binding with sulphite severely hampering adsorption (70% inhibition). To optimise gold desorption, preliminary batch studies indicated that a ratio of 1:1 of adsorbentdesorbent was optimal, whilst gas purging of thiourea with oxygen, air and nitrogen decreased gold elution in proportion to decreased amounts of oxygen. A series of desorbents were utilised, in column studies, to optimise and determine the speciation of bound gold. The presence of an oxidant with thiourea enhanced desorption greater than 3 fold when compared with thiourea alone. Thiourea desorption studies, aided by the oxidant, suggest that gold is present in the + I and 0 oxidation states. Ultimately thiourea, perchloric acid and hydrochloric acid was found to be the most optimal elutant for gold (J 00% recovery). For selective metal recovery oflead and copper, pre-washing the plant material with water, utilising an acid (0.3 M nitric acid), pumping in an up-flow mode, and recycling the desorbent six times was found to be optimal elutant for gold (J 00% recovery). Cost analysis of utilising elutant versus incinerating the biomass for gold recovery indicated the latter as the most economical. Over a 5 cycle adsorption and desorption series, acid desorption before each adsorption cycle was found to result in greater than 92% desorption for lead and 96% for copper. Gold recovery was 97% with incineration. A preliminary study with gold effluent (Mine C) indicated that nickel and sulphate was removed in batch and column studies. Gold removal was found to be 100% and 4% in batch and column studies respectively. Adsorption of gold in the effluent study was accompanied by the release ofHt. Modifying the plant material with various reagents failed to identify the primary binding sites and the role of polysaccharides, proteins and lipids in gold(ill) uptake. The mode of gold binding is suggested as being initially ionic, this is very rapid, with the interaction of the anionic complex, [AuCI₄]". with the cationic biomass (PH 2). This eventually leads to the displacement of the chloride ligand(s) initiating covalent binding. Spectral studies of the chemical interaction between gold and the representative tannins indicated the protonated hydroxy groups to be responsible. All evidence suggests that the binding mechanisms of gold are not simple. Preliminary adsorption studies of platinum by Azalia filiculaides were conducted. Batch studies indicated that J gIL biomass concentration, initial platinum concentration of 20 mgIL and pH 2 are optimal, while the column studies indicated a flow-rate of! 0 rnL/min and initial platinum concentration of 20 mgIL as optimal. In the platinum effluent study, platinum showed a removal of 23 % and 2 J % for the batch and column studies respectively. Again adsorption was accompanied by //' release. Azalia filiculaides demonstrated its feasibility in the removal of gold and platinum from simulated as well as waste water solutions. Its potential viability as a biosorbent was demonstrated by the high recovery from synthetic solutions of greater than 99% for gold (2-10 mgIL), and greater than 89% for platinum (20 mgIL).

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