Hydrometallurgy 56 2000. 323336 www.elsevier.

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Application of the shrinking core model to the kinetics of extraction of gold I/ , silver I/ and nickel II/ cyanide complexes by novel anion exchange resins
Greg W. Dicinoski a,1, Lawrence R. Gahan b, Peter J. Lawson c,) , John A. Rideout c
b c

School of Chemistry, Uniersity of Tasmania, Hobart, Tasmania 7001, Australia Department of Chemistry, Uniersity of Queensland, St. Lucia, Queensland 4072, Australia School of Chemical and Biomedical Sciences, Central Queensland Uniersity, Rockhampton, Queensland 4702, Australia

Received 27 May 1999; received in revised form 15 February 2000; accepted 21 February 2000

Abstract This paper describes an investigation of the kinetics of loading of goldI., silverI., and nickelII. cyanide complexes onto two novel anion exchange resins with high selectivity for the linear dicyanoaurateI. and dicyanoargentateI. complexes. The kinetic data fit well to a shrinking core theoretical model, and indicate that in all three complexes, the loading is controlled by the rate of diffusion of the ions penetrating the reacted layer. Diffusion coefficients were determined and those of AuI. and AgI. cyano complexes are similar to one another but much higher 30 to 60 times. those of the NiII. cyano complex on these two resins. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Aurocyanide; Argentocyanide; Gold and silver selective resins; Resin-in-pulp; Shrinking core model; Kinetics of loading of precious metals onto anion exchange resins

Corresponding author. E-mail addresses: greg.dicinoski@utas.edu.au G.W. Dicinoski., p.lawson@cqu.edu.au P.J. Lawson.. 1 Also corresponding author.

0304-386Xr00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 0 8 2 - 7

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1. Introduction Cyanidation of gold and silver ores has remained the dominant hydrometallurgical technology over the last century for economic recovery of these precious metals w1x. Very few significant technological improvements occurred in the industry in the first 70 years of the 20th century. The release of the price of gold however in 1968 from the fixed US$35roz gold standard resulted in a rapid tenfold increase in its price and the improved profitability of gold processing catalysed significant investment in research and development over the last 30 years. This has transformed precious metal recovery into a high tech hydrometallurgical process capable of economically extracting increasingly complex ore types and lower grades of ores. Zinc cementation of precious metals from cyanide leachates via the MerrillCrowe process has largely been replaced in the last 25 years. by carbon-in-pulp CIP. or carbon-in-leach CIL. concentration processes coupled with electrolytic recovery of the precious metals w2x. Despite this success, carbons lack of selectivity has triggered comparisons of CIP with resins-in-pulp RIP. over the last 15 years w38x. Although commercial anion exchange resins have been used at the Golden Jubilee Mine in South Africa w8x, and in the former Soviet Union w6x, economic viability was doubtful. However, the development of new gold specific resins at Mintek in South Africa w914x and elsewhere w1519x has rejuvenated interest in the RIP vs. CIP debate. Johns and Marsh w20x have recently presented convincing evidence that gold-specific resins are an economically viable alternative. Over 20 sterically hindered gold and silver cyanide selective quaternary ammonium functionalized anion exchange resins have been synthesised and characterised at the Central Queensland University CQU. w21,22x. The kinetics of the extraction of the AuI., AgI. and NiII. cyanide complexes by two of the most promising of these resins has been evaluated in this paper, and a Shrinking Core Model SCM. w2325x applied to the interpretation of this data. The structures and abbreviated names of the two resins of interest are illustrated in Fig. 1. Both resins are derivatives of polystyrenerdivinyl benzene polymers. NOTREN was synthesised by capping a tris2-aminoethyl.amine TREN. resin derivative. TEA-BE was synthesised by forming a tribenzyl ether of a tris2-hydroxyethyl.amine TEA. resin derivative w26x. These bulky mono-cationic sites selectively adsorb linear goldI. and silverI. cyanide complexes but reject the tetrahe-

Fig. 1. a. NOTREN resin, b. TEA-BE resin.

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dral and octahedral complexes of copperI., zincII., ironII. and III. and cobaltIII. and partially load the square planar nickelII. cyanide complex.

2. Experimental All acids and complexes used were of A.R. quality. The atomic absorption spectroscopic analyses were performed with either a Varian AA1475 or a Varian SpectrAA-300 spectrometer. Details of syntheses of the two novel resins used in this study and numerous other CQU resins. will be reported elsewhere w26x. These two resins were derivatives of polystyrene approximately 3% crosslinked with divinyl benzene and chloromethylated to 4 mmol Clrg dry. 2060 mesh. Polysciences Merrifield resin.. Confirmation of the syntheses was gained by FT-IR difference spectroscopy, CPrMAS 13 C NMR, anion exchange capacity tests and microanalyses. 2.1. Determination of the diffusion coefficient for each resin A shallow bed micro scale procedure similar to that of Riveros and Cooper w7x, which avoids the formation of a concentration gradient across the resin bed, was followed here. The resins of interest were screened to achieve uniform bead sizes, NOTREN to a size of 3040 mesh av. 0.51 mm. and TEA-BE to a size of 2530 mesh av. 0.66 mm.. NOTREN had a degree of substitution D of S. of 1.2 mmolrg dry. and TEA-BE a D of S of 0.92 mmolrg dry.. In each case, 0.025 g of dry resin in the chloride form was degassed in water and wet-loaded into a 120-mm long by 10 mm I.D. glass column and retained by a sintered glass frit. Solutions were passed through the resin beds at 200 mLrh, as follows: Au: 1000 mgrL Au as KwAuCN. 2 x 5 mmolrL Au., 130 mgrL KCN 2.0 mmolrL., 100 mgrL NaOH 2.5 mmolrL. at pH G 11 and 258C. Ag: 814 mgrL Ag as KwAgCN. 2 x 7.5 mmolrL Ag. q KCN and NaOH as above. Ni: 300 mgrL Ni as Na 2 wNiCN.4 x P H 2 O 5 mmolrL Ni. q NaCN and NaOH same molarity as above. Flow times of 5, 10, 20, etc., to 60 min were run on each column for each metal cyanide solution. The resins from each time period were filtered off, washed copiously with water and methanol and air-dried, then dried in a vacuum oven overnight at 508C. Each resin was completely digested in acid for quantitative metal ion analysis, a typical procedure for which follows: 0.10 g of loaded resin was charred in 10 mL of conc. sulphuric acid with heating in a fume cupboard. The temperature was then lowered below 1008C and 10 mL of conc. nitric acid added and the mixture reheated until digestion was complete. It was again cooled below 1008C and 10 mL of conc. hydrochloric acid added and the solution further heated to solubilise the gold. The solution was then cooled and diluted appropriately in a volumetric flask and the solution analysed for metal ions by atomic absorption spectroscopy.

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2.2. Determination of mass transfer coefficients for each resin and each metal cyanide complex The method used to determine the mass transfer coefficient is similar to that used in Section 2.1, but metal cyanide complex concentrations were one-tenth of those used previously and KCN and NaOH concentrations were unaltered: In each case, 0.50 mmolrL of M nq was used as metallocyanides, plus 130 mgrL KCN to give 2 mmolrL free cyanide. and 100 mgrL NaOH to give 2.5 mmolrL base. at pH G 11, at 258C.

3. Shrinking core mathematical model Ion exchange processes can be separated into two broad classes. The first contains the fast, reversible electrostatic exchange processes involving simple cations or anions, which occur uniformly between the ions in solution and the opposite ions of the porous solid phase. The second category includes those ion exchange processes, which are accompanied by fast chemical reactions, such as the abstraction of the metal cyano complexes, where the interacting ions progress in shells into the resin matrix. A sharp moving boundary between the reacted outer shell and the shrinking unreacted inner core can be observed during the ion exchange process. The likelihood of such a process occurring in spherical resin beads was proposed by Helfferich w27x and was later investigated in various processes. This section considers the hypothesis that the anion exchange of the gold, silver and nickel cyano complexes are accompanied by fast chemical reactions which are controlled by the diffusion of these complexes through the reacted layer of the resin beads. This will be achieved by employing the Shrinking Core Mathematical Model which was developed by Smuckler et al. w23,24x. A summary of this model as developed by these workers and modified by Riveros and Cooper w7x follows. Consider a spherical anion exchange resin bead of radius R in contact with an external solution containing an anion A, with a concentration of CA which for this trial remained essentially constant by experimental design.. As the ion exchange reaction takes place, a layer of adsorbed complex is formed on the surface of the unreacted bead. This layer is porous, so the reaction can continue by the diffusion of A ions through this layer and which subsequently takes part in a rapid reaction at the interface of the reacted layer and unreacted core. This process is illustrated in Fig. 2, where the development of the concentration gradient from CA to zero is traced. It was also assumed by Bischoff w28x that for a pseudo-steady state system, the rate of shrinkage of the unreacted core, d rcrdt, was small when compared to the velocity of diffusion of ion A through the product layer. The concentration gradient of reactant molecules at any shell radius, r, in the reacted layer was given by w23,24x: y d NA dt s 4p r 2 D dC dr

1.

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Fig. 2. Representation of the shell progressive mechanism in a spherical ion exchange bead Reprinted from Fig. 1 of Ref. w24x, with permission from Elsevier Science..

where D is the effective diffusion coefficient, in cm2rs, for A through the porous reacted layer. The initial boundary conditions for the above equation are: at r s R cm . , while at r s rc , Cs0 because the reactant is consumed as rapidly as it diffuses to the surface of the unreacted core. Thus, integration of Eq. 1. yields: d NA dt s 4p Rrc D CA R y rc C s CA mmolrg.

2.

As the reaction progresses, the decrease of the radius of the unreacted core accompanying the consumption of the liquid reactant develops as given by: d NA dt s r B 4p rc2 d rc dt

3.

where r B is the capacity of the resin in mmolrg. Equating Eqs. 2. and 3. and separating the similar variables yields: yr B

HR

rc

1 y rc

1 R

rc2 d rc s DCA

H0 d t

4.

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which upon integration will give the relationship between t and the decrease in the radius of the unreacted core as shown by: ts

r B R2
6 DCA

1y3

/ /
R q2 R

rc

rc

5.

The fractional conversion, a , of the ion exchange polymer, is the ratio between the measured and maximum capacity of the resin. This is also referred to as the fractional approach to equilibrium loading of the resin and has values between zero and one. a is determined experimentally and can be related to the radii, R, in Eq. 5. as given by: 1yas

/
R 1 y 3 1 y a .
2r3

rc

6.

Substituting Eq. 6. into Eq. 5. produces the rate expression in terms of the fractional approach to equilibrium for the resin loading: ts

r B R2
6 DCA

q 2 1 y a .

7.

Eq. 7. can be further modified to accommodate an ion exchange process where the stoichiometric number is not equal to one, by inserting, n, the number of sites on the resin occupied by the absorbing anion, A. The above equation can be rearranged to a form amenable to graphical representation, Eq. 8.. Plotting the fractional conversion term against time allows the determination of the diffusion coefficient D cm2rs. for the anion, A, through a resin matrix. Thus, this form of the equation modelling the shrinking core process is given as w7,25x: 1 q 2 1 y a . y 3 1 y a .
2r3

6 nDCA

rB r 2

8.

Eq. 8. is valid for systems in which fast chemical reactions are occurring, there is negligible resistance to diffusion from the Nernst layer, the external solution has an approximately constant composition and the anion exchange resin beads are of constant size and have spherical geometry. The shrinking core model also predicts that when low concentrations of metal complexes are used, a regime of film diffusion control applies. In this case, the fractional approach to equilibrium, a , exhibits a linear relationship with time, since the Nernst diffusion layer and the external solution concentration are constant. This is shown by:

as

3nK m CA

rB r

9.

where K m is the mass transfer coefficient cmrs. for each complex between the external solution and the resin beads w7x. Like the previous equations, this one is valid only if the concentration of the metal complex anion in the external solution is constant and the resins beads are spherical and of constant size.

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The shrinking core model and variations thereof have been widely used in the literature to describe the kinetics of reactions accompanying fluidsolid interactions, some examples of which involving resins or polymers are given in Refs. w2934x.

4. Results and discussion From earlier work using two- and three-element systems on NOTREN and TEA-BE resins, it was noticed that the gold complex loaded faster than the silver which in turn loaded much faster than the nickel complex. We propose that the small sizes of the gold and silver cyano complexes allow faster diffusion than is possible for the larger nickel cyano complex. With the aim of investigating these points further, the extraction of the three metal cyano complexes from single-element solutions was studied using the shallow bed technique on a micro scale w7x. In this procedure, an aqueous solution is passed through a thin layer of resin beads at a high flow rate. This method avoids the formation of a concentration gradient through the resin bed. The loading of each of the metal cyano complexes on the NOTREN resin is represented in Figs. 3 and 4. The first displays the loading in millimoles of metal adsorbed per gram of resin against time while the second portrays the fractional approach to equilibrium loading a . with increase in time. The graphs for the TEA-BE resin are not illustrated here, but were very similar to those for the NOTREN data. The fractional approach to equilibrium of the gold and silver cyano complexes is more rapid than for the nickel cyano complex despite the higher ionic charge on the

Fig. 3. Rate of loading of AuI., AgI. and NiII. cyano complexes at high metal concentration on the NOTREN resin.

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Fig. 4. Fractional loading rate of AuI., AgI. and NiII. cyano complexes at high metal concentration on NOTREN resin.

latter. The nickel cyano complex has a reaction stoichiometry of two, while the precious metal cyano complexes have values of one. The parabolic kinetics for the loading of the metal cyano complexes on the resin is consistent with those evidenced in other trials temperature, ionic strength, etc... They strongly suggest a particle diffusion-controlled extraction, since the concentration of the metal cyano complexes in the external solution remained constant throughout the trial. Fig. 5 shows that a plot of w1 q 21 y a . y 31 y a .2r3. x vs. time is a straight line. A linear regression analysis of the data for each resin, along with calculation of the diffusion coefficient for each metal complex, is presented in Table 1. The magnitude of the D values for the gold and silver cyano complexes are similar in the NOTREN resin, but the silver complex appears slightly more mobile in the TEA-BE resin matrix than in the gold complex. This could be explained by the slightly smaller size of the silver complex. These D values for the gold complex are approximately 60 and 30 times that of the nickel complex, on the NOTREN and TEA-BE, respectively. The D values for the silver complex are some 60 and 50 times those for the nickel complex on the NOTREN and TEA-BE, respectively. Values for D have been determined for the loading of the gold, silver and zinc cyano complexes by Riveros and Cooper w7x on DOWEX MSA-1 1.08 = 10y5 , 0.903 = 10y5, and 3.00 = 10y6 cm2rs, respectively.. From these values, it is observed that the diffusivity of the Td zinc complex is about one-third of that for the gold or silver complexes. The values for the gold and silver complex diffusivities within the DOWEX MSA-1 resin matrix are about half or less those for the NOTREN and TEA-BE resin matrices, presumably due to the differences in the individual adsorbent matrix composition. The crosslinking of the CQU resins is fairly low ; 3%. whereas that of the DOWEX MSA-1 macroreticular resin is considerably higher ; 12%.. The low D values for wNiCN.4 x 2y on the CQU resins

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Fig. 5. Application of the SCM for determination of the diffusion coefficients for the AuI., AgI. and NiII. cyano complexes on the NOTREN resin.

can be explained by the fact that it is square planar and has an n value of two two sites required for nickel adsorption. and these resins have quite low D of S, and highly sterically hindered cationic sites see Fig. 1.. The gel type CQU resins are highly selective for the linear dicyanoaurateI. and dicyanoargentateI. complexes which are presumably able to access a higher proportion of cationic sites than the more bulky tetracyanonickelateII. complex. Although the wZnCN.4 x 2y is tetrahedral and has an n value of two, and is considerably more sterically hindered than the gold and silver complexes, the lower selectivity of the DOWEX MSA-1 is probably caused by the more uniform pores in the macroreticular resin, the greater accessibility of these cations, and the lower steric hindrance of the trimethyl substituents on these quaternary ammonium sites. The selectivities of the NOTREN and TEA-BE for the precious metal cyano complexes are in agreement with the hypothesis of Green et al. w11x, that such selectivities increase as alkyl substituents on the ammonium group are enlarged. If these hypotheses are correct, then the value determined for D is both a measure of the selectivity of the resin and the diffusivity of the complex within the resin matrix. The

Table 1 Determination of the diffusion coefficients of the gold, silver and nickel cyano complexes on the NOTREN and TEA-BE resins Resin NOTREN Metal Gold Silver Nickel Gold Silver Nickel Intercept y0.025 y0.041 0.001 y0.046 y0.020 y0.001 r2 1.00 0.99 0.98 0.99 0.99 1.00 Slope hy1 . 0.689 1.090 0.024 0.909 1.016 0.039 n 1 1 2 1 1 2 D cm2 rs. 1.97=10y5 2.07=10y5 3.42=10y7 2.21=10y5 3.73=10y5 7.23=10y7

TEA-BE

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proximity of the intercept on the y-axis to zero in Fig. 5 indicates that the contribution from film diffusion was negligible. For this to be so, the value of the mass transfer or film diffusion. coefficient from the Nernst layer must be considerably larger than the diffusion coefficient. Mass transfer coefficients K m . were determined to test this assumption. To do this, the concentrations of the metal ions were one-tenth of those in the previous test, while the free cyanide and base concentrations remained the same. The results for this series of tests are displayed in Figs. 6 and 7 for the NOTREN resin. Again, only the NOTREN data is displayed due to the similarity between the two sets of results. Table 2 summarises data for both resins. The relationship between the resin loading mmolrg. and contact time is linear as shown in Fig. 6. The loading rates of the gold, silver and nickel cyano complexes on the NOTREN resin were 0.4357 mmolrgrh, 0.2838 mmolrgrh, and 0.04174 mmolrgrh, respectively and were 0.4190 mmolrgrh, 0.3757 mmolrgrh, and 0.05584 mmolrgrh, respectively for the TEA-BE resin. The linearity suggests a regime of film diffusion control since the Nernst diffusion layer and the external solution concentration are constant. The shrinking core model also predicts that in the case of film diffusion control, the fractional approach to equilibrium a bears a linear relationship with respect to time, as shown earlier by Eq. 9.. This is illustrated in Fig. 7. It is seen from the intercept on the y-axis of Fig. 7, theoretically zero from Eq. 9.. and the linear correlation r 2 ., that a good fit to the model was obtained with each resin for the three metal cyano complexes. Thus, the loading is also influenced by diffusion control. The K m values for the three metal complexes on each resin indicate that gold

Fig. 6. Rate of loading of AuI., AgI. and NiII. cyano complexes at low metal concentration on the NOTREN resin.

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Fig. 7. Fractional loading rate of AuI., AgI. and NiII. cyano complexes at low metal concentration for determination of mass transfer coefficients on NOTREN resin.

and silver complexes migrate to the resin bead surface about 10 times as fast as the nickel complex. Also, the gold complex moves faster than the silver complex despite its larger size. This can be explained by the more polarisable nature of the gold complex giving it a slightly higher effective negative charge than the silver complex. This result is the opposite of that obtained for the diffusion coefficient and supports the loading trends of these two complexes observed previously, with the initial loading rate of the gold complex being faster than that of the silver complex, while the final equilibrium loading of the two complexes are comparable. The results for these two CQU resins are comparable with those obtained by Riveros and Cooper w7x for the loading of the gold, silver and zinc cyano complexes on the DOWEX MSA-1 resin, 4.42 = 10y3 , 6.11 = 10y3 , and 3.53 = 10y3 cmrs, respectively.. Finally, the magnitude of K m for each complex on the two resins is much larger than the value for D by a factor of approximately 100 for the gold and silver complexes and 1000 for the nickel complexes..

Table 2 Determination of the mass transfer coefficients for the gold, silver and nickel cyano complexes loading on the NOTREN and TEA-BE resins Resin NOTREN Metal Gold Silver Nickel Gold Silver Nickel Intercept 0.0009 0.0089 0.0040 0.0136 0.0262 0.0087 r2 1.00 1.00 0.99 0.99 1.00 0.99 Slope hy1 . 0.363 0.284 0.070 0.454 0.407 0.121 n 1 1 2 1 1 2 K m cmrs. 4.09=10y3 2.67=10y3 3.92=10y4 5.08=10y3 4.09=10y3 6.77=10y4

TEA-BE

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This confirms that the loading is diffusion-controlled and is less influenced by the mass transfer of the anion to the Nernst layer. After studying the selectivity of several commercial weak and strong base anion exchange resins for wAuCN. 2 xy over base metal cyano complexes, Riveros w32x has suggested that the resin matrix has a significant bearing on such selectivity. He concluded that low hydrophilicity and a low ionic density isolated cationic sites. increase the affinity of a resin for wAuCN. 2 xy, whereas high hydrophilicity and a high ionic density increase resin affinity for the multivalent hydrated ions such as wCuCN.4 x 3y and wFeCN. 6 x 4y. Such relationships have also been discussed by Fleming and Cromberge w3x and Green et al. w10x. In this work, the resin matrices were held constant and although the polystyrenerdivinyl benzene matrix is quite hydrophobic, the quarternary ammonium derivatives are somewhat polar and hydrophilic and these resins would therefore have intermediate hydrophilicity. However, their low D of S or ionic density. and their sterically hindered cationic sites render them highly selective for the linear goldI. and silverI. cyano complexes. Hiskey and Ette w25x showed that the weak base resin, PAZ-4, designed especially to be selective for the gold and silver cyano complexes, also displayed behaviour consistent with the SCM. Their adsorption model relies on the exchange of all the chloride counter-ions on the resin by cyanide ions. This is assumed to also occur in the present study as the cyanide anion is present in a reasonable concentration ; 2.0 mmolrL., has a slightly larger ionic radius, and is more polarisable than the chloride ion. It is then assumed that the gold cyano complex is transported into the resin matrix by a bridging and billiard-ball mechanism. This mechanism is illustrated in Fig. 8 and functions by the

Fig. 8. Hiskey and Ettes w25x model depicting the mechanism of aurocyanide loading onto an anion exchange resin.

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Scheme 1. Reaction for the abstraction of the aurocyanide complex by an anion exchange resin according to the shrinking core model and the model of Hiskey and Ette w25x.

gold atom bridging between sites by co-ordinating with the adsorbed cyanide group already in place. The gold complex advances into the resin when an aurocyanide complex ion collides with a bridged gold atom already bound to the resin. Thus, the gold advances into the resin matrix by the collision and formation of RNCAuCN. bridges. This conclusion is consistent with the observed experimental data above, with the known lability of dicyanoaurateI. w35x and the shrinking core model. According to this mechanism, the loading of the gold cyano complex onto the strong base resin proceeds via the reaction presented in Scheme 1. This mechanism will also apply to the dicyanoargentateI. complex which is similarly labile.

5. Conclusion The initial extraction rates of these cyano complexes on the two CQU resins is controlled by liquid film diffusion. Gold and silver are extracted at considerably higher rates than nickel because of higher diffusivities in the liquid film. As the reacted layer increased in thickness, the extraction is controlled by particle diffusion in the resin matrix. The differences in resin diffusivities of these complexes were confirmed by fitting single element kinetic data to a shrinking core model. The diffusion coefficients of AuI. and AgI. cyano complexes are significantly higher than those of NiII. on these two resins. The selectivity of these resins for the precious metal cyano complexes is thought to be predominantly caused by the sterically hindered nature of the quaternary ammonium cationic sites.

Acknowledgements The authors are grateful for a Central Queensland University research grant, and one of us G.W.D.., for an Australian postgraduate award. They wish to gratefully acknowledge the generosity of Prof. J. Brent Hiskey of the University of Arizona for allowing use of Fig. 8 Fig. 13 of Ref. w25x., and for supplying a copy of this. They also are grateful to Elsevier Science for permission to use Fig. 2 Fig. 1 of Ref. w24x..

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