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The Dependence of Sorbed Copper and Nickel Cyanide Speciation on Ion Exchange Resin Type Versiane A

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The Dependence of Sorbed Copper and Nickel Cyanide Speciation on Ion Exchange Resin Type Versiane A Hydrometallurgy 61Ž. 2001 105–119 www.elsevier.nlrlocaterhydromet The dependence of sorbed copper and nickel cyanide speciation on ion exchange resin type Versiane A. Leao˜ a,1, Grant C. Lukey a, Jannie S.J. van Deventer a,), Virginia S.T. Ciminelli b a Department of Chemical Engineering, The UniÕersity of Melbourne, ParkÕille, Victoria 3010, Australia b Department of Metallurgical and Materials Engineering, UniÕersidade Federal de Minas Gerais. Rua Espırito´ Santo, 35. Belo Horizonte, MG, 30160.030, Brazil Received 17 October 2000; accepted 20 February 2001 Abstract The present study investigates the influence of functional group structure and resin matrix on the speciation of copper and nickel cyanides sorbed onto two commercially available ion exchange resins. Batch experiments were performed using synthetic copper and nickel solutions containing 50 and 200 mgrL free cyanide, respectively. Despite the presence of 2y 3y CuŽ. CN34 and CuŽ. CN in solution, it has been found using Raman spectroscopy that the Imac HP555s resin, which has a 2y polystyrene–divinylbenzene matrix, loads predominantly the CuŽ. CN3 complex. In contrast, the polyacrylic resin, 2y 3y Amberlite IRA958, sorbed significant amounts of both CuŽ. CN34 and CuŽ. CN . It has been found that the speciation of nickel cyanide sorbed onto each resin was the same. A recently developed mathematical model based on statistical thermodynamic principles has been used as a tool to understand further the equilibrium sorption of copper and nickel cyanide complexes onto each resin studied. A higher sorption energy for nickel compared to copper has been observed for the sorption onto Imac HP555s. In contrast, the sorption energy for copper was found to be higher than for nickel for the polyacrylic resin, Amberlite IRA958. The values of the model parameters obtained were correlated with the chemical features of each complex in solution as well as sorbed onto the resins. q 2001 Elsevier Science B.V. All rights reserved. Keywords: Copper cyanide complexes; Speciation; Raman spectroscopy; Ion exchange 1. Introduction The widespread presence of ores with low gold content as well as high levels of base metals is The processing of gold–copper ores is at present challenging the research community to identify and a major focus of attention in the minerals industry. develop new methods andror technologies for the cost-effective processing of these types of ores. The processing of gold–copper ores is currently under ) Corresponding author. Tel.: q61-3-8344-6620; fax: q61-3- investigation and some alternatives are being pre- 8344-4153. sented. Since the majority of copper minerals are E-mail address: [email protected]Ž. J.S.J. van Deventer . 1 soluble in cyanide solutions, chrysocolla and chal- Permanent address: Department of Metallurgical and Materi- wx als Engineering, Escola de Minas, Universidade Federal de Ouro copyrite being the main exceptions 1 , the main Preto, Minas Gerais, Brazil. challenge is to decrease the cyanide consumption 0304-386Xr01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S0304-386XŽ. 01 00159-1 106 V.A. Leao˜ et al.rHydrometallurgy 61() 2001 105–119 during leaching. Some alternatives have been pro- is important to identify the metal cyanide speciation posed such as the use of selective flotation, leaching because this information is used to estimate parame- with ammonia–cyanide solutions and also cyanide ter values in the mathematical model that has been recycling. developed to describe the equilibrium sorption be- In the case of cyanide recycling, the proposed haviour of each system studied. methods usually involve the acidification of cyanide As the sorption step is dependent on the physico- solutions. In the AVR process, the cyanide solution chemical features of both the solution and the resin it is acidified Ž.Acidification , then contacted with air in is necessary to assess the loading for different con- a counter-current tower to volatilise the soluble centrations of the metals in solution. This is particu- cyanide Ž.Volatilisation . Finally, the HCN–air mix- larly important in the case of the gold–copper ores ture is neutralised Ž.Reneutralisation in a caustic located on a transition zone between the sulphides at wx solutionŽŽ.. NaOH or Ca OH2 . Riveros et al. 2 the bottom of the mine and the upper part where the showed the feasibility of applying the AVR process oxide ore is found. This transition zone usually to solutions containing high amounts of copper presents a rather irregular copper contentwx 8 . In this cyanides. The standard AVR practice requires the regard, the modelling of these conditions allows the use of clarified solutions or barren bleeds. The appli- prediction of sorption equilibria when the concentra- cation of the AVR process to pulps must be done at tions of these metals in solution change significantly. higher pHŽ. usually 5.5 to 7.5 pH range . However, Many mathematical models have been proposed copper cyano-complexes start to decompose at a pH for the equilibrium sorption of ions onto soils, acti- lower than 3 and so the acidification in the above- vated charcoal and also ion exchange resins. These mentioned pH range does not allow the copper-bound models are effective in predicting the loading of the cyanide to be releasedwx 3,4 . sorbent in relatively simple systemsŽ no complex Recently developed resin technology can be used species in solution, homogeneous solid phase and for the recycling of cyanide from pulps as well as low ionic strength. However, they usually fail in from clarified solutions. In this process, ion ex- predicting sorption equilibria in more complex sys- change resins are used to sorb and concentrate the tems such as those found in hydrometallurgical oper- cyano-complexes that have been leached from the ations—high ionic strength, different complexes in ore. The resins are then screened from the pulp and solution. eluted. Current examples of this technology are the In the present work the mathematical model origi- Augment and the Vitrokele processeswx 5,6 . nally formulated by De Kockwx 9 has been used as a Leao˜ and Ciminelliwx 7 have studied previously tool to understand further the equilibrium sorption of the sorption of metal cyano-complexes onto strong copper and nickel cyanide onto two commercially base resins from solutions containing high concentra- available ion exchange resins. This model has re- tions of copper and minor amounts of iron and cently been used to describe the equilibrium sorption nickel. The objective of the work was to identify a of gold and copper cyanide onto a variety of ion suitable resin for cyanide recycling in the processing exchange resins in non-saline and highly saline solu- of gold–copper ores. It was observed by Leao˜ and tionswx 10,11 . It is based on the principles of statisti- Ciminelliwx 7 that resins having a polyacrylic matrix cal thermodynamics as well as the Metropolis Monte possess a greater affinity for copper cyanide com- CarloŽ. MMC numerical method. An important as- pared to nickel cyanide, while for polystyrene-based pect of this modelling approach is that it does not resins the converse is observed. It was proposed that use any solely empirical parameters. It is therefore this selectivity was due to the physico-chemical fea- possible to include fundamental information of the tures of each resinŽ. matrix and exchange groups and system in order to facilitate easier estimation of also the solution, however, no direct measurement of parameters. It is important to note that the emphasis metal speciation was undertaken. In the present work, of the current work is to compare the equilibrium Raman spectroscopy is used to determine the specia- sorption of copper and nickel cyanide onto ion ex- tion of copper and nickel cyano-complexes in solu- change resins for the purpose of recycling the bound tion and also sorbed onto each ion exchange resin. It cyanide. The two resins investigated have a different V.A. Leao˜ et al.rHydrometallurgy 61() 2001 105–119 107 functional group structure and also resin matrix. Amberlite IRA958Ž. 1 mL and Imac HP555s Ž 1 Therefore, the present work investigates the sorption mL. were loaded by contacting each resin with a of copper and nickel cyano-complexes on resins with solution containing 0.002 M copper and nickel different affinities for the metals. The effect of speci- cyanide. The amount of resin used was chosen in ation of each metal cyanide complex in solution as order to obtain significant sorption of each metal on well as sorbed onto the resin is discussed. The both resins. Potassium cyanideŽ. 98%, Aldrich was present study combines the results obtained from added to these solutions in order to increase the Raman spectroscopy and also the mathematical model concentration of free cyanide to approximately 50 or to develop for the first time a complete understand- 200 mgrL. Consequently, the CNrCu and CNrNi ing of the equilibrium sorption of copper and nickel molar ratio in these solutions was the same as the cyanide onto different ion exchange resins. solutions described previously. A Renishaw Raman MicroscopeŽ Ramascope 2000. was used to obtain the Raman spectra. A 2. Experimental procedures linearly polarised HeNe laserŽ Spectra Physics model a127, ls632.8 nm, 60 mW output. was used as 2.1. Ion exchange resins the excitation source. The Raman spectra of all Two commercially available ion exchange resins solutions were obtained by placing the cyanide solu- were selected for the sorption experiments. Both tions directly under the objective of the microscope. resins are macroporous and contain strong base qua- Optimum Raman spectra of each fluid were obtained = ternary ammonium functional groups. Imac HP555s by using a 5 objective to focus the laser source m is a polystyrene-based resin containing the trieth- approximately 10–20 m below the surface of the ylammonium as the exchange group.
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