Synthesis and evaluation of PGM-selective ligands
- Gxoyiya, Babalwa Siliziwe Blossom
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2013-05-28
- Subjects: Platinum group , Ligands , Ligands -- Evaluation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4450 , http://hdl.handle.net/10962/d1007849 , Platinum group , Ligands , Ligands -- Evaluation
- Description: A series of polydentate POM-selective, sulfur-containing amide ligands have been synthesized from ro-dibromoalkanes and mercaptoacetanilide, The resulting 3,6- dithiaoctanediamides and 3,7-dithianonanediamides, some of which contain a polymerisable group, were all characterized by high-resolution MS, IR, I Hand I3C NMR spectroscopic methods. Various approaches to the polymerisable ligands were explored, the most efficient proving to be the incorporation of an allyl ether moiety in the mercaptoacetanilide. The corresponding Pd(U) and Pt(II) complexes were also prepared from the metal chloride salts and characterized by elemental analysis and spectroscopic methods. The NMR data indicates that both the cis- and transcomplexes were formed, while the IR data indicates cis- coordination of the chlorine . ligands. Molecularly imprinted polymers (MIP's), prepared using platinum(II) mercaptoacetanilide and 3,6-dithiadiamide complexes, showed high selectivity for , , palladium(II) [in the presence of Pt(II), CoCII), Cu(II) and Ni(II)] as determined by . ICP-MS analysis. The more kinetically inert Pt(II) ions however, slowly displaced Pd(II), confirming the Pt(II) selectivity of the MIP's. Solvent extraction studies were conducted to explore the selectivity of the 3,6- dithiaoctanediamides and 3,7-dithianonanediamides for Pd(U) over CoCII), Cu(U) and Ni(II). The ICP-MS data indicate that, in general, equilibration was achieved within ten minutes and that the longer-chain amides were less selective than the shorter-chain analogues. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Authors: Gxoyiya, Babalwa Siliziwe Blossom
- Date: 2013-05-28
- Subjects: Platinum group , Ligands , Ligands -- Evaluation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4450 , http://hdl.handle.net/10962/d1007849 , Platinum group , Ligands , Ligands -- Evaluation
- Description: A series of polydentate POM-selective, sulfur-containing amide ligands have been synthesized from ro-dibromoalkanes and mercaptoacetanilide, The resulting 3,6- dithiaoctanediamides and 3,7-dithianonanediamides, some of which contain a polymerisable group, were all characterized by high-resolution MS, IR, I Hand I3C NMR spectroscopic methods. Various approaches to the polymerisable ligands were explored, the most efficient proving to be the incorporation of an allyl ether moiety in the mercaptoacetanilide. The corresponding Pd(U) and Pt(II) complexes were also prepared from the metal chloride salts and characterized by elemental analysis and spectroscopic methods. The NMR data indicates that both the cis- and transcomplexes were formed, while the IR data indicates cis- coordination of the chlorine . ligands. Molecularly imprinted polymers (MIP's), prepared using platinum(II) mercaptoacetanilide and 3,6-dithiadiamide complexes, showed high selectivity for , , palladium(II) [in the presence of Pt(II), CoCII), Cu(II) and Ni(II)] as determined by . ICP-MS analysis. The more kinetically inert Pt(II) ions however, slowly displaced Pd(II), confirming the Pt(II) selectivity of the MIP's. Solvent extraction studies were conducted to explore the selectivity of the 3,6- dithiaoctanediamides and 3,7-dithianonanediamides for Pd(U) over CoCII), Cu(U) and Ni(II). The ICP-MS data indicate that, in general, equilibration was achieved within ten minutes and that the longer-chain amides were less selective than the shorter-chain analogues. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
Screening of technologies for the recovery of rhodium (III) metal ions from a precious metal refinery wastewater
- Authors: Mack, Cherie-Lynn
- Date: 2005
- Subjects: Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3987 , http://hdl.handle.net/10962/d1004046 , Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Description: The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.
- Full Text:
- Date Issued: 2005
- Authors: Mack, Cherie-Lynn
- Date: 2005
- Subjects: Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3987 , http://hdl.handle.net/10962/d1004046 , Rhodium , Metal ions , Sewage -- Purification -- Metals removal , Platinum group
- Description: The selective recovery of rhodium from wastewaters, in which the metal would be otherwise lost, would be highly profitable if the process were suitably low-cost. Current recovery processes are generally high maintenance and high-cost, whereas biological processes can be engineered to run with little external input in terms of cost and maintenance. Three emerging technologies were chosen based on their reported efficiency when removing base metals from wastewaters. The first technology screened, the sulphide-extraction membrane bioreactor (SEMB), consists of a sulphate-reducing prokaryote (SRP) anaerobic digester, in which a silicone membrane is submerged. Wastewater is passed through the membrane and metal ions are precipitated as metal sulphides by the hydrogen sulphide gas, which is capable of permeating the membrane. The second technology screened was a fluidized sand bed reactor in which metal ions are removed from solution via induction of nucleated precipitation by sodium carbonate onto the sand grains. The third, and most well established removal technology screened was a biosorption system using immobilized Saccharomyces cerevisiae biomass as the biosorbent. Experimental trials with each technology highlighted drawbacks with each; the SEMB system proved to be largely ineffective when challenged with the removal of rhodium from the wastewater as the rhodium precipitate fouled the membrane within hours, the fluidized bed system seemed unable to overcome the acidity of the wastewater and thus could not precipitate out the rhodium metal, and the efficiency of the biosorption process was hampered by the diversity of rhodium species present in the wastewater, which reduced the amount recovered. The outcomes of the trials with each technology indicated that further optimization of the technology or pretreatment of the wastewater is necessary before any of these options can be implemented. It could be concluded, however, that despite further optimization, both the SEMB and the fluidized bed system were not applicable in this case as precipitation would be non-specific, resulting in the necessity for further steps in order to purify the rhodium ions. Hence, the biosorption system was shown to be most applicable, and further optimization of the system could yield a highly efficient rhodium recovery process.
- Full Text:
- Date Issued: 2005
Finite element simulations of shear aggregation as a mechanism to form platinum group elements (PGEs) in dyke-like ore bodies
- Authors: Mbandezi, Mxolisi Louis
- Date: 2002
- Subjects: Platinum group , Magmas , Shear flow , Geophysics , Terrestrial heat flow
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5561 , http://hdl.handle.net/10962/d1018249
- Description: This research describes a two-dimensional modelling effort of heat and mass transport in simplified intrusive models of sills and their feeder dykes. These simplified models resembled a complex intrusive system such as the Great Dyke of Zimbabwe. This study investigated the impact of variable geometry to transport processes in two ways. First the time evolution of heat and mass transport during cooling was investigated. Then emphasis was placed on the application of convective scavenging as a mechanism that leads to the formation of minerals of economic interest, in particular the Platinum Group Elements (PGEs). The Navier-Stokes equations employed generated regions of high shear within the magma where we expected enhanced collisions between the immiscible sulphide liquid particles and PGEs. These collisions scavenge PGEs from the primary melt, aggregate and concentrate it to form PGEs enrichment in zero shear zones. The PGEs scavenge; concentrate and 'glue' in zero shear zones in the early history of convection because of viscosity and dispersive pressure (Bagnold effect). The effect of increasing the geometry size enhances scavenging, creates bigger zero shear zones with dilute concentrate of PGEs but you get high shear near the roots of the dyke/sill where the concentration will not be dilute. The time evolution calculations show that increasing the size of the magma chamber results in stronger initial convection currents for large magma models than for small ones. However, convection takes, approximately the same time to cease for both models. The research concludes that the time evolution for convective heat transfer is dependent on the viscosity rather than on geometry size. However, conductive heat transfer to the e-folding temperature was almost six times as long for the large model (M4) than the small one (M2). Variable viscosity as a physical property was applied to models 2 and 4 only. Video animations that simulate the cooling process for these models are enclosed in a CD at the back of this thesis. These simulations provide information with regard to the emplacement history and distribution of PGEs ore bodies. This will assist the reserve estimation and the location of economic minerals.
- Full Text:
- Date Issued: 2002
- Authors: Mbandezi, Mxolisi Louis
- Date: 2002
- Subjects: Platinum group , Magmas , Shear flow , Geophysics , Terrestrial heat flow
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5561 , http://hdl.handle.net/10962/d1018249
- Description: This research describes a two-dimensional modelling effort of heat and mass transport in simplified intrusive models of sills and their feeder dykes. These simplified models resembled a complex intrusive system such as the Great Dyke of Zimbabwe. This study investigated the impact of variable geometry to transport processes in two ways. First the time evolution of heat and mass transport during cooling was investigated. Then emphasis was placed on the application of convective scavenging as a mechanism that leads to the formation of minerals of economic interest, in particular the Platinum Group Elements (PGEs). The Navier-Stokes equations employed generated regions of high shear within the magma where we expected enhanced collisions between the immiscible sulphide liquid particles and PGEs. These collisions scavenge PGEs from the primary melt, aggregate and concentrate it to form PGEs enrichment in zero shear zones. The PGEs scavenge; concentrate and 'glue' in zero shear zones in the early history of convection because of viscosity and dispersive pressure (Bagnold effect). The effect of increasing the geometry size enhances scavenging, creates bigger zero shear zones with dilute concentrate of PGEs but you get high shear near the roots of the dyke/sill where the concentration will not be dilute. The time evolution calculations show that increasing the size of the magma chamber results in stronger initial convection currents for large magma models than for small ones. However, convection takes, approximately the same time to cease for both models. The research concludes that the time evolution for convective heat transfer is dependent on the viscosity rather than on geometry size. However, conductive heat transfer to the e-folding temperature was almost six times as long for the large model (M4) than the small one (M2). Variable viscosity as a physical property was applied to models 2 and 4 only. Video animations that simulate the cooling process for these models are enclosed in a CD at the back of this thesis. These simulations provide information with regard to the emplacement history and distribution of PGEs ore bodies. This will assist the reserve estimation and the location of economic minerals.
- Full Text:
- Date Issued: 2002
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