This thesis explores the behaviour of metal cyanide complexes under oxidative acid conditions in ion exchange systems, with the objective of developing an ion exchange based process for the treatment of gold cyanidation tailings. The novel cyanide detoxification process developed from this study employs strong base ion exchange resins to extract cyanide from tailings. Variations in the stability of cyanide complexes are exploited to concentrate, recover, or destroy cyanide species loaded on the resin, through the use of an oxidative acid eluent containing H2O2 and H2SO4. This eluent removes all base metal cyanide complexes from strong base resins, while regenerating the resin. The spent eluent, containing the base metals recovered from the tailings, can be used as a source of such base metals. Copper can be recovered separately from other base metals if necessary. Low levels of precious metals present in the tailings are accumulated on the resin as the ion exchange bed is cycled between loading and elution stages. They can be recovered economically, so as to offset the cost of the tailings detoxification. Cyanide is initially concentrated as an alkaline solution, which can be detoxified within the process or recovered for recycling. This process was successfully tested at pilot scale by treating approximately 14,000 m3 of cyanide contaminated tailings solution, over 14 loading/elution cycles on a standard strong base ion exchange resin bed. This treatment reduced the total cyanide concentration of the contaminated solution from approximately 50 mg/L to an average of 1.5 mg/L. The reagent cost was approximately ADD 0.50 per m3 of treated liquor. When the resin was repeatedly loaded with mixed metal cyanide species and eluted with the oxidative acid eluent, a gradual deterioration of the ion exchange resin performance was noted. The reduction of net operating capacity of the columns due to resin deterioration was in the order of 1-3% per loading/elution cycle. The oxidation of resin catalysed by copper, the precipitation of metal hexacyanoferrates on the resin and the oxidation of Au(CN)2- to Au(CN)4- were identified as possible factors giving rise to the reduction of resin loading capacity.

Ion exchange equilibria are presented for [ ]??? ??? Au(CN)2 / Cl , [ ]??? ??? Au(CN)2 / SCN and SCN??? / Cl??? in aqueous solution, and in various mixed solvents, at 303K using Purolite A500 as the ion-exchanger. The mixed solvents investigated include water-acetone, water-dimethylsulfoxide (DMSO) and water-N-methyl-2-pyrrolidone (NMP). In aqueous solution, the selectivity of Purolite A500 for a given anion increases in the order: [ ]??? ??? &lt ??? &lt Cl SCN Au(CN)2 . This selectivity sequence confirms the high affinity of the ion exchange resin for the [ ]??? Au(CN)2 species. In mixed solvents, however, the selectivity of Purolite A500 for [ ]??? Au(CN)2 decreases with an increase in the composition of the organic solvent in the external solution. Mixed solvents containing greater than 60 mol% organic solvent are preferred for the displacement of [ ]??? Au(CN)2 from the resin. The effectiveness of a given type of mixed solvent generally increases in the following order: DMSO &it acetone &it NMP. The ion exchange equilibria are correlated using the Law of Mass Action, modified with activity coefficients, to determine the equilibrium constant for each binary system. The fitted values of the equilibrium constants are consistent with the trends observed in the ion exchange isotherms. The accuracy of the correlation results in the mixed solvent systems range from 1 to 10% and this is similar to the level of accuracy obtained for the ion exchange equilibria in aqueous solution. From these results it can be concluded that the Law of Mass Action is equally valid in mixed solvent systems. The variation in the equilibrium constant with mixed solvent composition, for a given binary system, correlates well with the dielectric constant of the mixed solvent. For a given value of the dielectric constant, however, the equilibrium constant, however, the equilibrium constant is dependent on the type of mixed solvent. A fundamental relationship is derived between the equilibrium constants and the Gibbs energies of transfer associated with the solvation of the ions in the mixed solvents. Based on this relationship, the redistribution of ions between the pore solution and the bulk mixed solvent, appears to be the most significant factor that governs the selectivity of the resin in mixed solvent systems.

Thesis (M. Sc.)--University of Hong Kong, 1996. / Includes bibliographical references (leaf 75-77).

Brandenburgische Techn. Universiẗat, Diss., 2003--Cottbus.

Thesis (MTech (Chemical Engineering))--Cape Technikon, Cape Town, 1999 / Carbon-in-pulp (CIP) and carbon-in-leach (CIL) remain the most effective, and widely used processes for gold recovery from cyanided pulps. The extensive use of carbon in such processes have prompted many researchers to investigate the mechanism of metal cyanide adsorption. Not only has this provided many viable theories in the understanding of the mechanism, but it has also led to an improved understanding of the effects of the various operating conditions on the CIP circuit. However, the declining gold price has made gold producers aware of the need to either further optimise existing circuits or find alternative means of operation so as to improve efficiency. It is therefore the aim of this study to investigate the factors which influence the metal extraction circuit. In this study the effects of parameters such as gold and carbon concentrations, slurry density and stirring speed on the adsorption process were investigated. It was found that the effects of gold and carbon concentrations could be determined directly, that is, a definite linear relationship exists between these two parameters and adsorption rate. However, slurry density and stirring speed (power input) have a twofold effect on the process. For this reason two distinct terms called the "blinding" and "mixing" numbers have been identified. It has been shown that all the parameters investigated influences the rate of adsorption during the constant rate adsorption period. However, only solution concentration, carbon concentration and carbon loading influence the process during the diminishing rate of adsorption. This confirmed the belief that intraparticle diffusion is the rate controlling factor during the diminishing rate period. Furthermore, the point at which constant rate adsorption is replaced by the diminishing rate of adsorption is mainly a function of solution concentration.

Thesis (MTech (Chemical Engineering))--Cape Technikon, Cape Town, 2000 / In a typical gold-recovery plant, it is estimated that a substantial amount of the gold in residues may be in the form that is recoverable by cyanidation. The gold in residues can be ascribed broadly to (l) the presence of cyanicides, which consume the cyanide radical and thus inhibit dissolution of gold, (2) refractory gold resulting from coatings on some gold particles, (3) large gold particles incompletely dissolved due to inadequate contact time, (4) unliberated gold as a result of too coarse a milled product, and (5) gold dissolved during leaching, then adsorbed by other minerals or by carbonaceous matter in the pulp. This study focuses on the latter, where dissolved gold is pregrobbed during leaching by adsorbent materials in the ore. The term pregrobbing refers to the active adsorption ofgold from cyanide pregnant solutions by components ofthe ore. It has been suggested that gold already dissolved by cyanide may be adsorbed by other minerals and by carbonaceous matter in the pulp. The presence ofcarbonaceous matter in gold ores presents a two-fold problem namely, the poor release of gold from the carbonaceous matrix and the uptake of dissolved gold by the carbonaceous leach residues. Studies by several other investigators using ores from various parts of the world have similarly shown that the natural carbonaceous matter associated with refractory gold ores often behaves like activated carbon when in contact with aurocyanide solutions. Some debate also exists over the extent to which gold may be adsorbed onto the surfaces of minerals. Different authors have identified that minerals such as' pyrite, copper sulphides, quartz and layered silicates, such as kaolin, phlogopite and ilIite exhibit gold adsorbing properties. Activated carbon was first used as a model pregrobber in batch kinetic adsorption experiments in the presence of a gold selective strong base anion-exchange resin.

Cyanide utilization in Pseudomonas fluorescens NCIMB 11764 occurs via oxidative conversion to carbon dioxide and ammonia, the latter satisfying the nitrogen requirement. Substrate attack is initiated by an enzyme referred to as cyanide oxygenase (CNO), previously shown to require components in both high (H) (>30 kDa) and low (L) (<10 kDa) molecular weight cell fractions. In this study, tetrahydrobiopterin (H4biopterin) was identified as a cofactor in fraction L, thus making CNO appear as a pterin- dependent hydroxylase. CNO was purified 150-fold (specific activity 0.9 U/mg) and quantitatively converted cyanide to formate and ammonia as reaction products. When coupled with formate dehydrogenase, the complete enzymatic system for cyanide oxidation to carbon dioxide and ammonia was reconstituted. CNO was found to be an aggregate of known enzymes that included NADH oxidase (Nox), NADH peroxidase (Npx), cyanide dihydratase (CynD) and carbonic anhydrase (CA). A complex multi-step reaction mechanism is proposed in which Nox generates hydrogen peroxide which in turn is utilized by Npx to catalyze the oxygenation of cyanide to formamide accompanied by the consumption of one and two molar equivalents of oxygen and NADH, respectively. The further hydrolysis of formamide to ammonia and formate is thought to be mediated by CynD. The role of H4biopterin and of the enzyme CA in the proposed process remains unclear, but the involvement of each in reactive oxygen and radical chemistry is consistent with the proposed formation of such species in the catalytic process. H4biopterin may additionally serve as a protein stabilizing agent along with a protein co-purifying with CynD identified as elongation factor Tu, a known chaperone. At least two of the CNO components (Nox and CynD) are complex oligomeric proteins whose apparent association with Npx and CA appears to be favored in bacterial cells induced with cyanide allowing their purification in toto as a multiprotein enzyme complex.

Cell-free extracts from Pseudomonas fluorescens NCIMB 11764 catalyzed the degradation of cyanide into products that included C02, formic acid, formamide and ammonia. Cyanide-degrading activity was localized to cytosolic cell fractions and was observed at substrate concentrations as high as 100 mM. Two cyanide degrading activities were identified by: (i) the determination of reaction products stoichiometries, (ii) requirements for NADH and oxygen, and (iii) kinetic analysis. The first activity produced CO2 and NH3 as reaction products, was dependent on oxygen and NADH for activity, and displayed an apparent Km for cyanide of 1.2 mM. The second activity generated formic acid (and NH3) pfus formamide as reaction products, was oxygen independent, and had an apparent Km of 12 mM for cyanide. The first enzymatic activity was identified as cyanide oxygenase whereas the second activity consists of two enzymes, a cyanide nitrilase (dihydratase) and putative cyanide hydratase. In addition to these enzymes, cyanide-grown cells were also induced for formate dehydrogenase (FDH), providing a means of recycling NADH utilized by cyanide oxygenase.

Fife and O'Shaughnessy have made a serices of di-esters by allowing the sodium salts of various fatty acids to react with ethyl monochloracetate according to the following equation: RCO2 Na + ClCH2 CO2 C2 H5 -----------> RCO2CH2CO2 C2 H5 + NaCL The mechanism of the reaction appears to be ionic and to involve the attack of an RCO2- ion on the carbon atom to which the chlorine atom is attached. As the RCO2- approaches this carbon atom the chlorine atom moves away and leaves as a chloride ion. This reaction appears to be similar to the Williamson synthesis of ethers: RONa + R'X --------------> ROR' + NaX

No description available.