M.S.

Ph. D.

The object of this investigation was to determine the transfer coefficients based on a “no loss” material balance, Viscosity Gravity Constant for each extraction and the contact area in conjunction with the material balance when a cylinder stock out of midcontinent oil was subjected to furfural refining in a one-inch in nominal diameter pyrex glass spray column using various ratios of furfural to oil. The oil was passed in tiny drops through the 9.75 feet high column countercurrent to the furfural flow which was down through the column. The average number of drops formed and the time of contact with the solvent was determined. From these values the average contact area in square feet at any moment was calculated. Two runs were made at high ratios of furfural to oil, and in these runs, no area of contact was determined. The column extractions were carried out at 75 ± 3°F. In order to determine the equilibrium values necessary for these calculations, batch extractions using the same ratio of solvent to oil were carried out at 230°F—at which temperature the furfural and the oil were miscible. The ratios of furfural to oil used were 2.35, 3.00, 3.53, 5.20, 9.24 and 14.20. The values of the transfer coefficient based on the “no loss” material balance varied from 0.0427 to 4.59 lbs./hr./cu.ft. of column volume/unit C as the ratio was increased. The values of the transfer coefficients based on the Viscosity Gravity Constant varied from 0.0520 to 6.28 lbs./hr./cu.ft. of column volume/unit C as the ratio was increased. The values of the transfer coefficient was based on the “no loss” material balance and the calculated contact area varied from 0.390 to 1.168 as the ratio was increased. The resultant values of the H.T.U.’s based on the three methods of calculation were good checks for the first two ratios and fair checks for the next two highest. For the ratio of 2.35:1.0 the H.T.U. based on the “no loss” material balance alone was 1.15, on the V.C.C. for each extraction it was 1.4 and for the method utilizing the contact areas and the “no loss” material balance it was 1.08 feet. The best batch refined oil had a viscosity index of 85. The best column refined oil had a viscosity index of 73.5. In both cases these values were reached using a ratio of 5.2 parts of furfural to one part of oil by weight and subsequent increases in this ratio did not improve the properties. / Master of Science

Several recent studies have shown that acid mine drainage (AMD) may be a promising source of rare earth elements (REEs), which are essential feedstocks for many high tech applications and defense products. AMD is a longstanding environmental challenge and is currently the primary pollutant of water in the Appalachian coal mining region. Acid generated during the coal mining process tends to leach several transition metals from the surrounding rock strata. While iron, aluminum, and manganese have traditionally been noted as the predominant metals in AMD, recent studies have also shown that REEs are also present, albeit in trace concentrations, often less than 5 μg/L. The recovery of REEs from AMD can be both an economic and environmental advantage; however, the low REE concentrations and high contamination from other metals makes the concentration and purification of REEs quite difficult. This research seeks to develop and optimize a process capable of producing mixed rare earth concentrates with purities exceeding 90% from an AMD feedstock. Parallel efforts by other members of the research team showed that a solid preconcentrate, nominally 0.1 to 2% REE, can be readily produced from AMD; however, that pre-concentration process cannot provide the further enrichment needed to generate high purity oxides suitable for downstream markets. In this project, solvent extraction was investigated as secondary process used to further enrich the low grade preconcentrate to a purity exceeding 90%. Initially, laboratory-scale batch solvent extraction tests were performed on synthetic REE solutions to determine the influence of various process parameters (e.g. pH, extractant dosage, diluent type, and feedstock concentration). Next, the separation of REEs from major AMD gangue elements was investigated using synthetic leachate solutions with concentrations similar to those expected from the pre-concentrate samples. This process showed that the grade targets could easily be met when combining optimal parameters from each step. From this preliminary work with synthetic solutions, an optimal SX process was developed and validated using a real leachate generated from a pre-concentrate sample. By integrating leachate preparation, solvent extraction, scrubbing, stripping, and oxalic acid precipitation, an oxide containing 90.5% rare earth oxides was generated. Details on the process development, experimental optimization, and opportunities for process improvement are described. / Master of Science / Rare earth elements (REEs) are essential for many modern industries, high-tech applications, and defense products. The U.S. consumes approximately 11% of the global REE demand; however, the US supply chain is heavily reliant on imported Chinese feedstocks. This lack of a domestic supply chain exposes the US to both price and supply volatility, which are prevalent in the international markets. This supply issue is further compounded by a lack of suitable domestic feedstocks. REEs are rarely concentrated into mineable ore deposits, and in some cases the extraction and processing of conventional REEs deposits entails considerable environmental risk. As a result of these challenges, numerous federal agencies and private companies have recently sought to identify promising alternative resources. One potential alternative resource is acid mine drainage (AMD), which is a common environmental challenge associated with coal and hard rock mining. Prior studies have shown that acid mine drainage contains REEs; however, other metals, such as iron, aluminum, and manganese, preclude REE recovery using conventional processing techniques. As such, the goal of this research is to develop and optimize a process capable of recovering and concentrating REEs from an AMD feedstock. The research conducted in this thesis predominantly included laboratory testing using synthetic AMD samples. The complexity of the synthetic AMD progressively increased from very simple, single element solutions to complex multi-component mixtures. Through this research, data and information from these controlled experiments was used to design a multi-step solvent extraction process capable of producing final REE products exceeding 90% purity. In the last stage of the research, the final process was validated using actual AMD recovered from an operating mine site. The validation test showed that the process was effective in meeting its initial objectives: the grade of the final rare earth oxide was determined to be 90.5%. This laboratory-scale experimental work represents the first step of process needed to develop and deploy a commercial technology capable of producing REE products from AMD feedstocks.

This investigation has led to the following conclusions: 1. Good removals of most bacterial species were observed. 2. Increased length of settling time increased the percent removal of pure cultures. 3. The solvent coagulation process worked best at a pH very near the pH produced by the bacteria during growth. 4. There was no advantage in changing from room temperature. S. proper surface active agents aided in the coagulation of bacteria in the solvent ooagulation process. 6. Almost all of the bacteria in suspension after the coagulation process were not viable. 7. Good removals were observed using the solvent coagulation process on mixed cultures. 8. The chlorinated solvent coagulation process shows promise for commercial operations. / Master of Science

Supercritical extraction of coal is removal of a select fraction of the coal by a solvent which is slightly above its critical temperature and above its critical pressure. The objective of this dissertation was to understand the mechanism of supercritical extraction, to test some promising solvents, and to explore the design implications of the findings. Supercritical extraction of Wyodak coal was studied by passing various solvents upwards through a 15-gram sample of 12-20 mesh coal. For the high temperature experiments, the coal was heated to 375°C and 425°C in a hot fluidized sand bath. The main solvent used was toluene, while extractions with n-pentane, xylene, methanol, and water were also done. The extract was fractionated into oils, asphaltenes, and asphaltols. Supercritical extraction of coal near pyrolysis temperatures affords an opportunity to remove unstable decomposition products from the reaction environment to avoid repolymerization and pore blinding. Stronger aromatic solvents removed the decomposition products as they were formed. However, product degradation even with the strongest solvents was inevitable during the initial few minutes. For the low temperature experiments (below 95°C), the solvent was carbon dioxide. Effects of liquid entrainers (pre-mixed with the coal), and heat-pretreatment of the coal (at 400°C for 1 hour) were also studied. The major difference between the high and low temperature extractions was that coal reactions occurred at high temperatures simultaneously with solubilization. Extraction of raw coal and heat-pretreated coals with carbon dioxide was negligible. However, extractions as high as 12% were possible when small amounts of liquid entrainers such as pyridine, toluene, and tetralin were pre-mixed with the coal. The entrainers were almost completely recovered with the extract. The process design implications of the supercritical extractions of coal were studied using the method developed by ESCOE (Engineering Societies Commision On Energy Inc.). Preliminary design estimates showed that the following supercritical extraction processes were possible alternatives to present commercialization efforts and deserve further attention: 1. Gasification of the extraction residua; 2. Satellite plants operating in parallel with coal-burning utilities; 3. Entrainer-aided extraction. / Ph. D.

Woven textile fabrics were designed and constructed from hydrophilic and hydrophobic spun yarns to give planar substrates containing amphiphilic microchannels with defined orientations and locations. Polypropylene fibers were spun to give hydrophobic yarns, and the hydrophilic yarns were spun from a poly(ethylene terephthalate) copolyester. Water wicking rates into the fabrics were measured by video microscopy and longitudinal wicking tests from single drops and from reservoirs. Intra-yarn microchannels in the hydrophilic polyester yarns were shown to selectively transport aqueous fluids, with the flow path governed by the placement of the hydrophilic yarns in the fabric. Simultaneous wicking of an aqueous and hydrocarbon fluid into the hydrophilic and hydrophobic microchannels of an amphiphilic fabric was successfully demonstrated. The high degree of interfacial contact and micron-scale diffusion lengths of such co-flowing immiscible fluid streams inside amphiphilic fabrics suggest potential applications as highly scalable and affordable microcontactors for industrial liquid-liquid extractions. The efficiency of liquid-liquid extractions carried out with the amphiphilic fabrics was evaluated. Solvent extraction efficiencies were shown to reach up to ~98%.

Niobium (Nb) and tantalum (Ta) are found in the same group (VB) of the periodic table of elements and therefore have similar chemical properties, which is the reason why they are difficult to separate. They are usually found together in various minerals of which the most important are columbite ((Fe, Mn, Mg)(Nb, Ta)2O6) and tantalite ((Fe, Mn)(Nb, Ta)2O6). Several methods have been used to separate Nb and Ta. Most methods use very high concentrations of hydrofluoric acid (HF) and sulphuric acid (H2SO4) as the aqueous phase, tributyl phosphate (TBP) as the extractant and methyl isobutyl ketone (MIBK) as the organic phase. High extraction can be achieved, but the reagents used are hazardous. With the increasing demand of both pure Ta and Nb, as well as stricter environmental requirements, a need exists to develop a more efficient and safer technique to separate Ta and Nb. In this project the focus was on the solvent extraction (SX) of Ta and Nb with the possible application in a membrane-based solvent extraction (MBSX) process. For this purpose, eight different extractants were investigated, namely the cation exchangers di-iso-octyl-phosphinic acid (PA) and di-(2-ethylhexyl)-phosphoric acid (D2EHPA), the neutral solvating extractant 2-thenoyl-trifluoro- acetone (TTA), and the anion exchangers Alamine 336, Aliquat 336, 1-octanol, 2-octanol and 3-octanol. The extractant to metal ratio was varied from 0.1:1 to 10:1, while cyclohexane was used as diluent and 3% v/v 1-octanol was used as modifier for the organic phase. In addition, four different acids, hydrochloric acid (HCl), nitric acid (HNO3), sulphuric (H2SO4) and perchloric acid (HClO4), were used at different concentrations to determine the best combination for extraction. First, fluoride salts of Ta and Nb (Ta(Nb)F5) were tested and the optimum results showed that the highest extraction was obtained with PA and D2EHPA, irrespective of the type of acid used. Similarly, irrespective of the acid used, extraction with PA and D2EHPA increased with increasing acid concentration, followed by Alamine 336, Aliquat 336 and then TTA and the octanols. Extraction values of 97% Ta at 15 mol/dm3 and 85% Nb between 12 and 15 mol/dm3 were obtained. Although extraction of both Ta and Nb was achieved with all the acids tested, only H2SO4 showed sufficient separation (log D = 3) of the two metals in the 0 to 2 mol/dm3 acid range and 15 mol/dm3 for PA and D2EHPA, respectively. Precipitation, probably due to hydrolysis of the metals, occurred in the absence of acid when using Alamine 336, Aliquat 336 and TTA. The octanols showed the least amount of extraction of Ta and Nb, irrespective of the acid investigated. The optimum extraction was achieved with an E/M ratio of 3:1 of PA and D2EHPA as the extractant and 10 mol/dm3 H2SO4 in the aqueous phase. The NH4Ta(Nb)F6 salt solution was investigated using the optimum conditions for maximum extraction obtained from the Ta(Nb)F5 experiments, i.e. 4 mol/dm3 H2SO4 with an E/M ratio above 3:1 for the extractant PA and 4 mol/dm3 H2SO4 with an E/M ratio of 20:1 for the extractant D2EHPA. Kinetic equilibrium for PA was reached after 10 minutes and for D2EHPA after 20 minutes. The highest extraction of Ta (100%) above 3 mol/dm3 H2SO4 and Nb (54%) at 8 mol/dm3 with the highest separation factor of 4.7 with PA was achieved, followed by the 100% extraction of Ta above 5 mol/dm3 and 40% Nb at 10 mol/dm3 with the highest separation factor of 4.9 in D2EHPA. Although the aim of this study was the extraction and separation of Ta and Nb, the recovery or back extraction of the metals from the organic phase, as well as the membrane-based solvent extraction (MBSX) was briefly investigated. From the preliminary results obtained it became apparent that further research into the different aspects, including the type of stripping agent used, stripping agent concentration, effect of Ta to Nb ratio and different sources of Ta and Nb is needed to obtain the optimum conditions for the MBSX process and the subsequent recovery of Ta and Nb. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

Niobium (Nb) and tantalum (Ta) are found in the same group (VB) of the periodic table of elements and therefore have similar chemical properties, which is the reason why they are difficult to separate. They are usually found together in various minerals of which the most important are columbite ((Fe, Mn, Mg)(Nb, Ta)2O6) and tantalite ((Fe, Mn)(Nb, Ta)2O6). Several methods have been used to separate Nb and Ta. Most methods use very high concentrations of hydrofluoric acid (HF) and sulphuric acid (H2SO4) as the aqueous phase, tributyl phosphate (TBP) as the extractant and methyl isobutyl ketone (MIBK) as the organic phase. High extraction can be achieved, but the reagents used are hazardous. With the increasing demand of both pure Ta and Nb, as well as stricter environmental requirements, a need exists to develop a more efficient and safer technique to separate Ta and Nb. In this project the focus was on the solvent extraction (SX) of Ta and Nb with the possible application in a membrane-based solvent extraction (MBSX) process. For this purpose, eight different extractants were investigated, namely the cation exchangers di-iso-octyl-phosphinic acid (PA) and di-(2-ethylhexyl)-phosphoric acid (D2EHPA), the neutral solvating extractant 2-thenoyl-trifluoro- acetone (TTA), and the anion exchangers Alamine 336, Aliquat 336, 1-octanol, 2-octanol and 3-octanol. The extractant to metal ratio was varied from 0.1:1 to 10:1, while cyclohexane was used as diluent and 3% v/v 1-octanol was used as modifier for the organic phase. In addition, four different acids, hydrochloric acid (HCl), nitric acid (HNO3), sulphuric (H2SO4) and perchloric acid (HClO4), were used at different concentrations to determine the best combination for extraction. First, fluoride salts of Ta and Nb (Ta(Nb)F5) were tested and the optimum results showed that the highest extraction was obtained with PA and D2EHPA, irrespective of the type of acid used. Similarly, irrespective of the acid used, extraction with PA and D2EHPA increased with increasing acid concentration, followed by Alamine 336, Aliquat 336 and then TTA and the octanols. Extraction values of 97% Ta at 15 mol/dm3 and 85% Nb between 12 and 15 mol/dm3 were obtained. Although extraction of both Ta and Nb was achieved with all the acids tested, only H2SO4 showed sufficient separation (log D = 3) of the two metals in the 0 to 2 mol/dm3 acid range and 15 mol/dm3 for PA and D2EHPA, respectively. Precipitation, probably due to hydrolysis of the metals, occurred in the absence of acid when using Alamine 336, Aliquat 336 and TTA. The octanols showed the least amount of extraction of Ta and Nb, irrespective of the acid investigated. The optimum extraction was achieved with an E/M ratio of 3:1 of PA and D2EHPA as the extractant and 10 mol/dm3 H2SO4 in the aqueous phase. The NH4Ta(Nb)F6 salt solution was investigated using the optimum conditions for maximum extraction obtained from the Ta(Nb)F5 experiments, i.e. 4 mol/dm3 H2SO4 with an E/M ratio above 3:1 for the extractant PA and 4 mol/dm3 H2SO4 with an E/M ratio of 20:1 for the extractant D2EHPA. Kinetic equilibrium for PA was reached after 10 minutes and for D2EHPA after 20 minutes. The highest extraction of Ta (100%) above 3 mol/dm3 H2SO4 and Nb (54%) at 8 mol/dm3 with the highest separation factor of 4.7 with PA was achieved, followed by the 100% extraction of Ta above 5 mol/dm3 and 40% Nb at 10 mol/dm3 with the highest separation factor of 4.9 in D2EHPA. Although the aim of this study was the extraction and separation of Ta and Nb, the recovery or back extraction of the metals from the organic phase, as well as the membrane-based solvent extraction (MBSX) was briefly investigated. From the preliminary results obtained it became apparent that further research into the different aspects, including the type of stripping agent used, stripping agent concentration, effect of Ta to Nb ratio and different sources of Ta and Nb is needed to obtain the optimum conditions for the MBSX process and the subsequent recovery of Ta and Nb. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013.

With current energy demands globally and locally, nuclear energy remains one of the top competitors for cleaner and sustainable energy. The nuclear industry requires more inherent safety and proliferation resistance in reactor design. Thorium has therefore been identified as a possible fuel for future nuclear reactors that can comply with these requirements. However current extraction techniques are expensive, time consuming and generate large quantities of hazardous waste. A possible alternative to conventional solvent extraction of thorium is SFE (Supercritical Fluid Extraction). A monazite sample from the Steenkampskraal mine was investigated using SEM (Scanning Electron Microscope) analysis methods to determine the distribution of thorium in the grains that could potentially complicate the effectiveness of the SFE extraction method if zoning is present. The results show a homogeneous distribution with no discernable zonation in the grains. The concentration of Th, Ce and Nd was determined by quantitative MPA (Micro Probe Analysis). The results obtained from the MPA point analysis on several grains show average Th, Ce and Nd concentrations of 6.5 wt. %, 24.1 wt. % and 9.7 wt. % respectively. The extraction of Th+4 from a filter paper was conducted to verify the extraction procedure and extractability of transition elements employing SFE. The extraction was conducted using supercritical CO2 and methanol as co-solvent with TBP (Tributyl Phosphate) and HFA (Hexafluoroacetylacetone) added in situ as chelates. ICP-MS results for the Th+4 extraction procedure showed extraction efficiency of 53 % compared to 83 % in literature (Kumar et al. 2009). This marked difference in extraction efficiency is attributed to ineffective trapping methods employed and lack of prior maintenance and support on the extraction apparatus. Subsequently all further extracted samples of Th from monazite were tested using XRF analysis methods. Due to the lack of prior maintenance on the extraction apparatus several technical breakdowns were encountered and addressed from a mechanical engineering standpoint. The operational effectiveness of the modified apparatus was verified through the extraction of marula seed oil and compared with another supercritical fluid (SF) extractor to show 50 % extraction efficiency in each case. A review of the literature indicated that the crystal chemical requirements for substitution of trivalent (Ce+3) for tetravalent (Th+4) may be fulfilled during SFE processes. Experimental substitution extractions were conducted by addition of different chelates and were conducted by subjecting the monazite samples to 20 MPa pressure for 180 min static flow and 10 min continuous flow extraction times with a CO2 flow rate of 2 mL/min with 10 % co-solvent flow rate. The results of the two sets of substitution extractions namely α and β show no clear indication of Th extraction. The maximum theoretical efficiency obtainable under current extraction equipment limitations was calculated as 12%. The XRF analysis error margin was given by the analytical laboratory as 10 %. The literature has shown the substitution of trivalent cations for tetravalent cations in the monazite structure to be a valid reaction mechanism. The experimental results showed little or no success in extracting thorium from monazite. In order to prove the practical feasibility of thorium extraction several changes to the experimental operating conditions is required. / MIng (Mechanical Engineering), North-West University, Potchefstroom Campus, 2015