Hydrometallurgy 64 (2002) 43 48 www.elsevier.

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Thiocyanate solutions in gold technology

A.G. Kholmogorov a, O.N. Kononova b, G.L. Pashkov a, Y.S. Kononov a,*
a

Institute of Chemistry and Chemical Technology, Siberian Department of the Academy of Science, Karl Marx Str. 42, Krasnoyarsk 660049, Russia b Department of Chemistry, Krasnoyarsk State University, Svobodny Pr. 79, Krasnoyarsk 660041, Russia Received 15 February 2001; received in revised form 22 January 2002; accepted 22 January 2002

Abstract The scope for using KSCN solutions in the field of gold leaching from chemical preparation products of hard arsenopyrite concentrates is shown. More than 95% gold is recovered in weak acidic solutions (pH = 2 5) at KSCN concentration 0.4 mol/L. The thiocyanate complexes are recovered on carbon adsorbents (BAU, UC, LKAU-4) as well as on ion exchangers (AV-17-10P, AP-100). The gold recovery degree is 99.2 99.8%. The desorption of gold from ion exchangers can be done by thiocarbamide solutions in H2SO4 at room temperature, and from carbon adsorbents by basic thiocarbamide solutions at f150 C. D 2002 Elsevier Science B.V. All rights reserved.
Keywords: Thiocyanate solutions; Gold; Carbon adsorbents; Ion exchangers; Thiocarbamide

1. Introduction The problems of gold recovery from hard coaly sulphide concentrates are discussed in our works (Kononova et al., 2000; Kholmogorov et al., 2000). Thiosulphate, cyanide and thiocarbamide solutions are used for the dissolution of gold from the products of chemical preparation (Kononova et al., 2000; Kholmogorov et al., 1999; Kononov et al., 2000). At the same time, a number of investigators (Barbosa and Monhemius, 1989; Mineev and Panchenko, 1994; Chursanov et al., 1993, 1997; Brukvin et al., 1999) propose to use, besides the above-mentioned reactants, thiocyanate solutions for gold leaching from ores, concentrates and products of chemical prepara-

tion. Thiocyanate solutions possess lower toxicity in comparison with sodium and potassium cyanides and better stability in various media. Moreover, they can be regenerated and obtained as a by-product in technological processes (Mineev and Panchenko, 1994; Chursanov et al., 1993). That is why we have applied thiocyanate solutions to the recovery of gold from the products of chemical preparation, which are similar to the products described in our papers (Kononova et al., 2000; Kholmogorov et al., 2000).

2. Experimental In the present investigation, we have used the goldcontaining products after the chemical preparation of arsenopyrite concentrates. The contents of iron sulphides and carbon-containing compounds in these products were about 0.1 0.2%, the gold content was f110 g/t.

Corresponding author. Tel.: +7-3912-27-38-31; fax: +7-391223-86-58. E-mail address: cm2@ktk.ru (Y.S. Kononov).

0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 0 4 - 3 8 6 X ( 0 2 ) 0 0 0 0 5 - 1

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Table 1 Physical chemical properties of the ion exchangers investigated Characteristics Ion exchangers AV-17-10P Type Functional groups Strong basic NCH3 3

AP-100 Medium basic NCH3 3 NCH3 2

ANKF-5 Polyfunctional

total for weak basic groups Total pore volume (cm3/g) Specific surface (m2/g) Exchange capacity for gold (mg/g) Manufacturer

Static exchange capacity (mmol/g)

4.4 0.2 0.47 42 3.9 4.3 TOKEM, Russia

3.9 3.2 1.2 29 3.4 3.6 Purolite Int., U.K.

5.4 3.8 0.55 33 2.9 3.1 Cherkassy, Ukraine

The leaching was accomplished in thermostatted reactors with vigorous mixing and predefined parameters:


certain concentrations of KSCN, Na2S2O3, NaCN, thiocarbamide;  weight ratios of solid to liquid phase 1:10 1:20;  process temperature 20 F 1 C.

The process of leaching continued for 3 5 h. After that, the analysis of gold was carried out: the contents of gold in solutions were determined by atomic absorption method (AAS-30, Germany), and the solid residues were analyzed in solutions obtained after the decomposition of samples in acids mixture (molar ratio HCl/HNO3 = 3:1). The analysis data were used for the calculation of the gold leaching rate from the chemically prepared

Table 2 Physical chemical properties of the carbon adsorbents investigated Characteristics Carbon adsorbent UC Grain size (mm) Mechanical strength (%) Total pore volume (cm3/g) Filled mass (bulk) (g/cm3) Specific surface (m2/g) Exchange capacity for 0.6 2.8 93 95 0.52 0.53 1040 4.1 31 2.1 2.2 Cocoa stones South African Republic BAU 1.9 3.1 81 84 1.2 0.53 530 5.9 47 2.3 2.4 Charcoal Ural district, Perm, Russia LKAU-4 0.8 1.2 87 94 0.82 0.50 590 4.8 28 1.9 1.8 Anthracite Kuznetsk district, Kemerovo, Russia

I2 (mmol/g) methylene blue (mg/g) gold from KSCN solutions (pH = 2.3) (mg/g)

Initial raw material for synthesis Deposit

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products: the amounts of gold recovered from the samples were at first expressed as metal amount per ton of the product (g Au/t), and then as gold contents recovered per unit time (v = g Au/t h). The logarithmic rate values (log v) were also used. The gold concentration from the solutions after the leaching was carried out on ion exchangers and on carbon adsorbents. Their physical chemical and sorption characteristics are summarized in Tables 1 and 2. The sorption properties of the sorbents were determined under batch experiment conditions. The distribution coefficients (D) were calculated from: mmol of Au sorbed per g dry sorbent mmol of Au sorbed per mL of solution

The equilibrium time for the sorption of gold from the thiocyanate solutions was 8 h. The molar ratio of the sorbent mass to the volume of the contacting solution was 1:5 1:500. The gold concentration in solutions was determined by atomic absorption method, and the contents of gold in the carbon adsorbents were calculated from the difference between the initial and equilibrium concentrations of gold in solutions. Gold contents in the ion exchangers were determined analogously. Moreover, the quantities of ion exchangers were ashed for 1 h at 550 600 C and then dissolved in the mixture of HCl + HNO3 (3:1) in order to determine gold concentration by atom absorption method. The initial form of the sorbents was chloride and sodium on anion and polyfunctional resins. The gold desorption was carried out by thiocarbamide solutions in H2SO4 (0.5 M Thio + 0.5 M H2SO4). All experiments were repeated three or four times. The experimental error for all experiments did not exceed 6%.

We have compared the rates of gold leaching by solutions of different complex-forming reactants. This leaching was carried out for the products of chemical preparation of arsenopyrite concentrates in nitric acid solutions (this preparation is described by Kononova et al., 2000). The results of these comparative experiments are shown in Fig. 1. It can be seen from Fig. 1 that thiocyanate solutions can be used for gold leaching from raw materials. The dissolution rate of gold in the KSCN solutions is slightly lower than that in sulphuric acidic thiocarbamide solutions (Fig. 1, curves 1 and 2). We have mentioned above (see Experimental) that the leaching process was carried out with vigorous mixing, aiming to make the process to run mostly in kinetic mode. During the process, the concentration of Fe3+ was f0.015 mol/L (in accordance with optimal conditions determined by Panchenko et al., 1975). The dissolution rate of gold from product in the thiosulphate solution is lower than in KSCN solution (Fig. 1, curves 2 and 3). It is known (Abbruzzese and Fornari, 1995) that the increase in the concentration of

3. Results and discussion The Au SCN H2O system is considered by Barbosa and Monhemius (1989) as an alternative to cyanide leaching for the recovery of gold from mineral raw materials. These authors have found that the most effective gold recovery takes place at pH = 1 3 and at SCN concentration 0.01 0.5 mol/L.

Fig. 1. Dependence of the gold leaching rate from the chemical product by solutions of the complex-forming reactants: 1 thiocarbamide (0.2 M Thio + 0.2 M H2SO4); 2 KSCN (0.4 mol/ L; pH = 2.2); 3 Na2S2O3 (0.5 mol/L; pH = 6.0); 4 NaCN (0.05 mol/L; pH = 11.3). Temperature is 20 F 1 C.

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tion on activated carbons or electrolysis for the isolation of gold from the thiocyanate solutions. We have used for this purpose the methods of ion exchange recovery on organic resins and adsorption on carbon adsorbents (Fig. 3; Tables 1 and 2). It can be seen from Fig. 3 that pH < 6 is more effective for the gold sorption both on ion exchangers and on carbon adsorbents. It can also be noted from the experimental data shown in Fig. 3 that the carbon adsorbents absorb the thiocyanate gold complexes to a greater extent than the ion exchangers (curves 1 3). Among the
Fig. 2. Dependence of the leaching rate of gold from the chemical product by KSCN solutions on pH value of solution. CKSCN = 0.4 mol/L; process time is 4 h.

Na2S2O3 to more than 0.2 mol/L has no effect on gold dissolution rate if the process time is less than 6 h. In this case, the diffusion limitations of the gold dissolution rate are reduced (CNa2 S2O3!0.2 mol/L) and the kinetic mode predominates (Abbruzzese and Fornari, 1995). The gold leaching in the cyanide solutions proceeds much slower in comparison with the sulphurcontaining reactants (Fig. 1, curve 4). It is stated (Kononov et al., 2000) that the gold dissolution is controlled by diffusion conditions in this case. It should be noted that f87% recovery of gold from product is achieved in NaCN solutions during 89 96 h (in comparison with 3 6 h required for other reactants). We have found that 89 93% recovery degree of gold from product can be reached in the weak acidic KSCN solutions (0.4 mol/L) in 4 5 h. Using a more basic medium, the gold dissolution rate decreases (Fig. 2). Therefore, the thiocyanate gold leaching from the chemically prepared arsenopyrite concentrates should be used in weak acidic medium (pH < 5) and at KSCN concentration 0.1 0.4 mol/L. We have obtained leach solutions containing up to 17.9 24.1 mg/L gold (without recycling). pH values of these solutions were 1.8 3.4, the concentration of iron(III) was up to 0.5 g/L and the contents of other elements were below 1 mg/L. Barbosa and Monhemius (1989), Chursanov et al. (1993) and Brukvin et al. (1999) propose to use precipitation methods (cementation) as well as sorp-

Fig. 3. Dependence of distribution coefficients of gold thiocyanate complexes on pH of contacting solution. CKSCN = 0.4 mol/L; 1 BAU; 2 UC; 3 LKAU-4; 4 AV-17-10P; 5 AP-100; 6 ANKF-5.

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carbon adsorbents, BAU (based on charcoal) reveals the best sorption properties and compares favorably with UC, which is recommended by manufacturers in the South African Republic for industrial use (this carbon adsorbent is supplied to Russia for the recovery of gold from cyanide solutions). The carbon adsorbent LKAU-4 (based on anthracite) is close to UC in its sorption properties (Fig. 3, curve 3). The gold recovery degree on the carbon adsorbents under the batch experiment conditions is 99.2 99.8% at pH = 2.2 2.3. The organic ion exchangers AV-17-10P, AP-100 and ANKF-5, which we also have used for the sorption of gold in our investigations, have a porous structure. Among them, AV-17-10P possesses the best sorption characteristics (Fig. 3, curve 4). The gold recovery degree on this resin is close to that on carbon adsorbents. Thus, the presence of strong basic functional groups in the ion exchanger is the principal factor under these conditions. Due to the lower content of such groups, the anion exchanger AP-100 is at

a disadvantage in relation to AV-17-10P (Fig. 3, curve 5). For the same reason, the polyfunctional amphoteric ion exchanger ANKF-5 absorbs the gold thiocyanate complexes to a considerably lower degree (Fig. 3, curve 6). It is known (Golodkov and Yelshin, 1999; Yelshin et al., 1999) that the desorption of gold from activated carbons can be carried out in autoclave-cured processes. The gold complexes absorbed on the ion exchangers can be desorbed by sulphuric acidic thiocarbamide solutions (Conradie, 1995). We have investigated the gold desorption from ion exchangers and carbon adsorbents by 3 11% thiocarbamide solutions in 3 4% H2SO4 (Fig. 4). It can be seen from the results obtained that the gold desorption degree is not more than 15% for the carbon adsorbents and about 99 100% for the ion exchangers (at 6 8% thiocarbamide). Aiming to increase the desorption degree of gold from the carbon adsorbents, we have used basic thiocarbamide solutions (0.5 0.8% NaOH) and elevated the process temperature up to 145 150 C (Golodkov et al., 1999). As a result, the gold desorption degree became 91 94%. Therefore, the carbon adsorbents as well as anion exchangers AV-17-10P and AP-100 can be recommended for the recovery of gold thiocyanate complexes.

4. Conclusions The gold leaching from products of chemical preparation of hard arsenopyrite concentrates by KSCN solutions was studied. It was shown that more than 95% gold recovery is achieved using weak acidic solutions (pH = 2 5). The KSCN concentration is 0.4 mol/L. The rate of gold leaching was compared for the different complex-forming reactants: thiocarbamide in H2SO4, Na2S2O3, KSCN, NaCN. It was found that the leaching rate in KSCN is slightly lower than that in thiocarbamide solutions and is much greater than that in NaCN or Na2S2O3 solutions. Moreover, the sulphur-containing reactants compare favorably with NaCN. The gold can be recovered from the thiocyanate solutions by sorption on carbon adsorbents and on ion exchangers. The complete desorption of gold was carried out on ion exchangers by sulphuric acid thiocarbamide solutions at the room temperature and on

Fig. 4. Effect of thiocarbamide concentration on gold desorption from carbon adsorbents (1, 2) and ion exchangers (3 5). 1 UC; 2 BAU; 3 AV-17-10P; 4 ANKF-5; 5 AP-100.

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A.G. Kholmogorov et al. / Hydrometallurgy 64 (2002) 4348 Kholmogorov, A.G., Kononov, Y.S., Pashkov, G.L., 1999. Vyshchelachivanie Zolota Sernokislymi Rastvorami Thiomocheviny iz Produktov Chimicheskoy Podgotovki Upornykh Uglerodsoderzhashchikh Arsenopyritnykh Konzentratov. 1st Siberian Symposium Zoloto Sibiri: Geologiya, Geochimiya, Technologiya, Economica. Book of Abstracts, Krasnoyarsk, Dec. 1 3. Ofset, p. 149 (in Russian). Kholmogorov, A.G., Kononov, Y.S., Pashkov, G.L., 2000. Azotnokislotnoe Vskrytie Upornykh Zolotosoderzhashchikh Uglistykh Konzentratov. Khimiya v Interesakh Ustoichivogo Razvitiya 8, 439 443 (in Russian, with English Abstract). Kononov, Y.S., Pashkov, G.L., Kholmogorov, A.G., 2000. Ob Ionoobmennom Izvlechenii Zyanistylh Komplexov Zolota. Khimiya v Interesakh Ustoichivogo Razvitiya 8, 444 448 (in Russian, with English Abstract). Kononova, O.N., Kholmogorov, A.G., Kononov, Y.S., Pashkov, G.L., Kachin, S.V., Zotova, S.V., 2000. Sorption recovery of gold from thiosulphate solutions after leaching of products of chemical preparation of hard concentrates. Hydrometallurgy 59, 153 157. Mineev, G.G., Panchenko, A.F., 1994. Rastvoruteli Zolota i Serebra v Hydrometallurgii Metallurgiya, Moscow, 241 pp. (in Russian). Panchenko, A.F., Kakovsky, I.A., Khmelnizky, O.D., 1975. Kinetika Rastvoreniya Zolota i Serebra v Vodnykh Rastvorakh Thiomocheviny. Izvestiya Akademii Nauk SSSR, Metally 6, 32 37 (in Russian, with English Abstract). Yelshin, V.V., Golodkov, Y.E., Leonov, S.V., 1999. Intensification of noble metal desorption from activated carbons. Materials of the Conference RAMM-99, Penang, Malaysia, pp. 704 711.

carbon adsorbents by basic thiocarbamide solutions at f150 C.

References
Abbruzzese, C., Fornari, P., 1995. Thiosulphate leaching for gold hydrometallurgy. Hydrometallurgy 39, 265 276. Barbosa, O., Monhemius, A., 1989. Thermochemistry of thiocyanate systems for leaching gold and silver ores. Precious Metals89: Proc. Int. Symp. TMS Ann. Meet. Las Vegas, Feb. 27 March 2. Pergamon, pp. 307 339. Brukvin, V.A., Vysozkaya, T.N., Levin, A.M., 1999. Povedeniye Blagorodnykh i Zvetnykh Metallov v Rodanistykh Electrolitakh pod Deistviem Peremennogo Toka. Izvestiya RAN, Metally 1, 11 14 (in Russian, with English Abstract). Chursanov, Y.V., Gamasonova, E.Y., Kakovsky, I.A., 1993. Rastvorenie Zolota v Kislotnykh Rastvoralh Rodanidov. Izvestiya RAN, Metally 4, 54 58 (in Russian, with English Abstract). Chursanov, Y.V., Potashnikov, Y.M., Gromova, S.V., 1997. Kinetika Rasyvoreniya Zolota i Serebra v Vodno-azetonovykh Rastvorakh Thiocyanata Kaliya. Journal Phisicheskoy Chimii 71, 1397 1400 (in Russian, with English Abstract). Conradie, P.J., 1995. Gold desorption from strong basic selective resin and its precipitation. Hydrometallurgy 37, 349 366. Golodkov, Y.E., Yelshin, V.V., 1999. Otlichitelnye Osobennosti Desorpzii Razlichnykh Komplexov Zolota i Serebra s Aktivnykh Ugley. Obogashchenie Rud, Metallurgiya, Irkutsk, pp. 37 40 (in Russian).