The purpose of this study was to investigate the process optimization of combined high pressure acid leaching (HPAL) and mixed hydroxide precipitation (MHP) route for the extraction of nickel and cobalt from &Ccedil / aldag lateritic nickel ore. In order to extract nickel and cobalt values into pregnant leach solution (PLS), several process parameters of HPAL including acid load, temperature, leaching duration and particle size were investigated in comparative manner at constant solid concentration and agitation speed. After HPAL trials, it has been found that more than one combination of parameters offered higher than 90% extraction efficiencies for both nickel and cobalt. Among them, 0.325 kg/kg acid load, 250&deg / C, 1 hour duration and 100% -1 mm particle size was selected as the optimum conditions with 94.1% Ni and 94.0% Co extractions. A stock of PLS was prepared under the stated conditions that was treated by downstream operations in order to obtain MHP. Initially by two-stage iron removal of downstream operations major impurities iron, chromium and aluminum were nearly completely removed with acceptable nickel and cobalt losses from PLS. Then, the nickel and cobalt were precipitated by two-stage mixed hydroxide precipitation. In the first step of MHP, the optimum conditions were chosen as pH=7.10, 60&deg / C and 1 hour duration. The intermediate product obtained at these conditions contained 44.3% Ni, 3.01% Co with 3.06% Mn contamination. In summary, it was found that &Ccedil / aldag nickel laterite ore was readily leachable under HPAL conditions and PLS obtained was easily treatable in order to produce saleable MHP.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

The aim of this study was to produce zirconium diboride (ZrB2) and other metal borides such as lanthanum hexaboride (LaB6) and cerium hexaboride (CeB6) by magnesiothermic reduction (reaction of metal oxide, boron oxide and magnesium) using volume combustion synthesis (VCS) and mechanochemical process (MCP). Production of ZrB2 by VCS in air occurred with the formation of side products, Zr2ON2 and Mg3B2O6 in addition to MgO. Formation of Zr2ON2 was prevented by conducting VCS experiments under argon atmosphere. Wet ball milling was applied before leaching for easier removal of Mg3B2O6. Leaching in 5 M HCl for 2.5 hours was found to be sufficient for removal of MgO and Mg3B2O6. By MCP, 30 hours of ball milling was enough to produce ZrB2 where 10% of excess Mg and B2O3 were used. MgO was easily removed when MCP products were leached in 1 M HCl for 30 minutes. Complete reduction of ZrO2 could not be achieved in either production method because of the stability of ZrO2. Hence, after leaching VCS or MCP products, final product was composed of ZrB2 and ZrO2. Formation of LaB6 and CeB6 were very similar to each other via both methods. Mg3B2O6 appeared as a side product in the formation of both borides by VCS. After wet ball milling, products were leached in 1 M HCl for 15 hours and pure LaB6 or CeB6 was obtained. As in ZrB2 production, 30 hours of ball milling was sufficient to form these hexaborides by MCP. MgO was removed after leaching in 1 M HCl for 30 minutes and the desired hexaboride was obtained in pure form.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Bottom ash (BA), generated from the incineration of municipal solid waste (MSW), contains valuable elements which present a potential economic incentive to attempt recovery. The first study of this thesis investigated the physical, chemical, and mineralogical characterization of MSWI-BA samples through a number of experiments. To develop a proper physical characterization of the BA material, the sample was ground and subjected to particle size distribution, wet magnetic separation, and a float-sink test. As for the chemical and mineralogical characterization, the sample was subjected to XRD, XRF, SEM-EDX, and elemental composition analysis. Additionally, sequential chemical extraction and acid-leaching tests were conducted. The results from this section revealed that carrying out a combination of beneficiation processes using the MSWI-BA sample previously classified into the coarse, middle, and fine-size fractions could lead to better metal concentration yield and recovery optimization. The wet magnetic separation showed outstanding metallurgy indicators towards Fe, with enrichment ratios close to 2.0 and recovery values near to 80%. Metals such as Cu and Co were also enriched by 1.51 and 1.66, respectively, suggesting that the magnetic separation performance and enrichment are a function of the bound of multi-metallic oxides fractions. The 2.95 SG density test reached enrichment ratios higher than 2.0 in Fe, Cu, Co, and Ni in the coarse fraction of the BA fraction, which decreases when reducing the size fraction. When reducing the density cutoff, the results showed that the sink fraction yield increased as the medium density decreased, and the enrichment ratios of the minor elements (Mn, Co, Ni, Sn, and V) were similar across the different size fractions. Complementary information was obtained by the mineralogical characterization of the enriched streams from the physical concentration test, which explains the results obtained. The Cu speciation and mineral phases identified were copper oxide, copper sulfate, and cupric sulfite. While the main Fe-rich constituents existed in chemical forms of iron oxides, such as magnetite, hematite with substituted varieties, spinel group, and metallic inclusions. The enrichment ratios of Mn, Cr, Cu, and Ni obtained through magnetic separation can be explained by the presence of metallic inclusions, where these elements exhibit an affinity for the iron-bearing particles. The acid leaching test revealed that metals such as Fe, Mn, Co, Cu, and Zn can be efficiently leached using 1M HCl within 30 min of the reaction. The second part of this research study constituted the evaluation of the effect of the particle size reduction, which was performed to assess the intraparticle heterogeneity of MSWI BA. The evaluation consisted of particle size reductions by crushing and grinding for different residence times and then subjecting the sample to a sequence of physical concentration tests, such as particle size distribution, froth flotation, and wet magnetic separation. Additionally, the elemental composition after each test was determined through ICP-MS analysis to compare the particle size effect in the recovery and concentration of the valuable elements. The elemental composition results revealed that the comminution process promotes the interaction of Fe, Zn, and Cu, in the fine fraction, by generating more surface area. In contrast, the minor elements were not significantly enriched by reducing the size fraction, suggesting that the comminution process does not impact the mobility and redistribution of the elements in low concentrations. The froth flotation performed in this study showed that when using 0.338 g/ton diesel as a collector, adjusting and controlling the pH between 8.8 to 9.2 throughout the test, the organic matter content can be efficiently reduced in the BA sample from 14.73% to 4.25% when the sample has been previously ground for 30 min. Slight enrichment ratios were observed in the concentrate stream of the froth flotation, suggesting that these elements are associated with the organic matter in the BA sample. In contrast, the wet magnetic separation results revealed significant enrichment ratios of Fe, Mn, Co, and Ni after 10 min of grinding. / Master of Science / The Bottom Ash (BA) generated by the incineration of household solid waste has been identified as a promising source of valuable elements. However, a comprehensive understanding of the BA sample's properties is required in order to determine the most suitable mineral processing method to enrich the elements. The first study of this research consisted of evaluating BA ash's physical, chemical, and mineralogical properties in the BA sample. Following the characterization study, the effect of particle size, as a function of the grinding time, in the valuable elements' enrichment was evaluated. The results suggest that Ti, Fe, Cu, and Zn are the major and most valuable elements, while Mn, Co, Ni, Sb, and V are valuable elements in a minor concentration in the BA samples. Some elements, such as Ti, Sc, Co, Mn, Ni, Sn, and V, have been declared by the US Department of the Interior as critical minerals due to their economic importance and vulnerability to supply chain disruption. Although Fe and Cu are not considered critical minerals, their consumption in 2022 was 40 and 1.9 million metric tons, respectively. The development of national industry and enhancing the understanding of the alternative sources for the valuable elements present an opportunity to diversify local suppliers, pursue a vertical integration of the economic model, and reduce the third-party international vendors' dependency. Likewise, this research supports the aims to reduce the demand for primary natural resources and contribute to the circular economy model, in which energy, resources, and material are kept in a lifecycle while reducing landfilling disposal.

A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

Bayer processing of bauxite employed for production of alumina yield a residue red-mud. The worldwide annual-rate of red-mud generation is approximately 120 million tons, and most of this is stockpiled. Red mud is rich in elements like aluminum, titanium and rare earths, in addition to the major iron-bearing constituents. The objective of this research is to explore such a strategy to extract Iron as fine particulate magnetite. Pyrometallurgical reduction experiments using carbon mixtures and a novel hydrometallurgical route are experimented. Reduction experiments performed with petroleum coke as a reductant resulted in incomplete reduction. The ‘optimal conditionsÂ’ for gaseous state reduction are determined to be: a processing temperature of 540oC ± 10oC, partial pressures CO (g) and CO2 (g) each of 0.070atm (bar) ± 0.001atm.(bar)/ inert diluent-gas: N2 (g), for a conversion-time of 30min. A mathematical-model was developed on the basis of unidirectional-diffusion of CO2 (g) within the CO2 (g)–CO (g)–N2 (g) gas-phase of the porous product-layer. Magnetic separation applied to the optimally reduced sample in: obtaining a magnetic portion with high iron and non-magnetic portion containing nonferrous (Al, Ti) is not successful. This finding was subsequently attributed to the nanometer length-scales crystallites of the predominant iron-containing phase, hydrated ferric-oxide(s) as determined by STEM micrographs. In addition, the presence of substitution for Fe3+ by Al3+ and Ti3+/4+ are determined with the help of MÖssbauer spectrograms. A hydrometallurgical route involving selective leaching and precipitation of iron in red-mud is tried. Red-mud is leached in oxalic acid at: 95˚C, 15 % Pulp density, 2.5 h leaching time, 1.5 pH. Kinetic studies yielded the leaching mechanism to be predominantly fluid film control. Ferric oxalate in the leach liquor is reduced to insoluble ferrous oxalate selectively using Iron powder. The ferrous oxalate formed is ~98 % pure. The precipitated ferrous oxalate is magnetically separated and reduced in Nitrogen atmosphere to form fine particulate magnetite. Additionally an economic feasibility study was conducted for the hydro and pyro alternatives to produce magnetite using Monte Carlo Simulations by imparting uncertainties in various input cost components. A traditional process was also compared to the proposed approaches for Total Capital Investment (TCI), Total Product Cost (TPC), Net Present Value (NPV) and sensitivity analysis. ~52 % reduction in Total product cost, 46 % reduction in Total Capital Investment was achieved for the hydrometallurgical process when compared to the traditional approach.

This research explored different catalytic cracking zeolite additives to improve propylene selectivity and minimize dry gas yield. A comprehensive study of the effect of zeolite structure, pore system and crystal size on maximizing propylene production in FCC unit and the effect of post synthetic modifications on the physicochemical properties and cracking activity of ZSM-5 was investigated using X-ray diffraction (XRD), pyridine adsorption fourier transform infra-red (FTIR), 27Al and 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) and the catalytic cracking using n-heptane, as a model compound for heavy naphtha. The catalytic performances of these additives were evaluated in a fixed-bed reactor unit using n-heptane as a model compound for naphtha at temperatures 450 - 500 oC and W/F 38 - 92 gcat.h/mol. A range of zeolites were tested with ZSM-5 showing the optimum results at high feed conversion. Further studies on ZSM-5 crystal size illustrated that nano ZSM-5 (300 nm) was superior compared to the regular ZSM-5 (2000 - 4000 nm) in achieved conversion level and propylene selectivity. These improvements were attributed to the shorter path lengths for the reactant reducing diffusion constraints significantly. Modifying nano ZSM-5 acidity using steaming, acid leaching and silanation showed significant improvement over nano ZSM-5 parent. Mild steaming of nano ZSM-5 improved both n-heptane conversion and propylene selectivity whilst severe steaming only improved propylene selectivity. This work attempted to address the often discussed catalytic activity enhancement from mild steaming and identified newly created moderate acid sites as the source of increased activity. Dealumination by acid leaching decreased the total aluminium content of nano ZSM-5 and changed the Brønsted/Lewis ratio. Increasing the B/L ratio, increased the conversion and propylene selectivity. In addition, this research focussed for the first time on the silanation of nano ZSM-5 and its effect on n-heptane cracking, in particular, propylene and dry gas selectivity. Silica was deposited on the external surface of nano ZSM-5 neutralising the acidic sites and as a result, dry gas yield was significantly decreased due to the elimination of non-selective cracking. However, the trade off with conversion was high.

Car exhaust catalysts were introduced in the early 1980’s, to limit the release of pollutants such as hydrocarbons, carbon monoxide and nitrogen oxides. These catalysts contain noble metals such as palladium (Pd), platinum (Pt) and rhodium (Rh) and are able to simultaneously abate all three of the above-mentioned pollutants, hence the name three-way catalyst (TWC). The exposure to high temperatures (800-1000 °C) during operation and the presence of additives in gasoline and lubricants will, after a certain time, lower the activity of the TWC. High temperatures reduce the active area by causing the noble metals to agglomerate and sinter, whereas the additives alter the activity either by fouling the pores of the support material or by interacting with the metals. The main objective of this work was to develop a method which allows for the removal of contaminants (additives) from the washcoat and enables the redispersion of the active sites (noble metals), in an effort to recover lost catalyst activity. For this purpose, regeneration experiments were carried out on a wide spectrum of different commercial car exhaust catalysts. The influence of a thermal treatment in a controlled gas atmosphere, such as oxygen or hydrogen, and a redispersing agent, e.g. chlorine, on the activity of TWC was investigated by means of laboratory-scale activity measurements. Several complementary characterization methods such as SEM/TEM, XRD, BET, LA, XPS and TPR were employed to verify the effects of the regeneration treatments on the catalyst morphology (Papers I, II). The results show that partial regeneration of catalyst activity and noble metal dispersion was achieved after thermal treatment in an oxygen-chlorine rich atmosphere at temperatures below 500 °C. A wet-chemical regeneration treatment with dilute oxalic and citric acid solutions is evaluated in Paper III. These acidic solutions are able to dissolve and remove contaminants from the washcoat, thus partly restoring the catalyst activity. An investigation of the effects of an oxy-chlorine thermal treatment for regeneration of a ‘full-scale’ commercial automotive three-way catalyst was carried out (Paper IV). Improved catalyst activity for a high mileage catalyst could be observed, with emissions lowered by approximately 30 to 40 vol.% over the EC2000 driving cycle. The properties of fresh, aged and regenerated catalysts were then studied by means of labscale experiments, on a local as well as a global level using a mathematical model (Paper V). The model allows for comparison of the intrinsic properties of the active surface by deriving and tuning parameters of a fresh catalyst and verifying the activity of a regenerated or aged catalyst. / QC 20100812