Materials Transactions, JIM, Vol. 30, No. 3 (1989), pp. 165 to 174 Silver Recovery from the Oxidative Leaching Residue of Copper Anode Slime* By Koichi Arai**, Sumiko Sanuki**, Norio Minami*** and Satos! sunada** ‘The feasibility of an electrolytic silver recovery process for oxidative leaching residue of Cu-anode slime with more than 37 mass% Ag component was investigated from the electrochemical and Kinetic aspects based on the experimental results of a leaching test, the stoichiometric determination of the elec trolytic silver recovery and the measurements of the rest potentials of Ag and Cu electrodes and the cathodic polarization curves for Pt electrode in a thiosulfate solution containing the complex ions of Ag(S,03); Cu(S,05);~ and Pb(S,0}):". From the electrochemical consideration and experimental study, it is concluded that a new elec- trolytic silver recovery process for the oxidative leaching residue of Cu-anode slime is available, and that the cathodic current efficiency for the Ag deposit from the thiosulfate solution containing Ag(S,0;)}~ ions is more than 94% and high purity of 9.8% metallic silver can be recovered. (esi Desember 5, 1988) Keywords: electrolytic silver recovery, oxidative leaching residue of copper-anode slime, thiosulfate leaching, electrochemical reaction, kinetics, cathodic polarization. I. Introduction The recovery process for precious metals such as Au, Ag and Pt from the complex sulfide ores and copper anode slime is based on the traditional pyrometallurgical treatments and the hydrometallurgical treatment such as cyanide leaching. However, with the growing awareness of the emissions detrimental to the enviroment, non-polluting and energy efficient processes are being investigated to either replace or modify the traditional pyromet- allurgical treatments. In this context the pres- ent study was undertaken to examine the feasibility of a new electrolytic silver recovery process for the oxidative leaching residue of Cu-anode slime which contains more than 37 mass% Ag component. The literature indicates that a few studies on the use of chlorine gas, acidic thiourea and * This paper was originally published in Japanese in J. Japan Inst. Metals, 3 (1989), 399. Department of Metallurgical Engineering, Faculty of Eng., Toyama University, Toyama 930, Japan, Graduate Student, Toyama University, Toyama 930, Japan thiosulfate as the leachant for the Cu-anode slime including a few Kinetic measure- ments, However, the hydrometallurgical treatment process for the precious metals is not well understood and no detailed study for the elec- trolytic silver recovery from the oxidative leaching residue of Cu-anode slime is available, In the present study, a new electrolytic silver recovery process for the oxidative leaching residue of Cu-anode slime was investigated from both an electrochemical and a kinetic point of view. Il. Electrochemical and Thermodynamic Considerations In estimating of the electrolytic silver recovery process for the oxidative leaching residue of Cu-anode slime and the electro- chemical reactions for the Ag deposit from the thiosulfate solution containing complex ions of Ag(S:03)3~, Cu(S:0,)§" and Pb(S:0))F, it is important to understand the conditions necessary for the required electrochemical reac- tions and the stable species in the thiosulfate166 solution containing the complex ions of Ag(S:0;)}", Cu(S,0,)~ and Pb(S.0,)3". For this purpose, the reactions of interest were thermodynamically assessed as a function of pH, the reduction potential and the ac- tivities of the reactants based on the available thermodynamic data, However, there is no available datum for Pb(S:0;)3- ion, and thus the free energy AG%s for Pb(S,03)} was calculated by using log 6!" for Pb(S:03)3 and the available thermodynamic data”, ‘The calculated stability relations amongst the metallic thiosulfate complex ions in the solution are shown in Fig, 1 for a temperature of 298K. The activities, a, of total dissolved complex ions and the total sulfur species were assumed to be 5x 10-* and 10°, respectively. The diagram shows that the reduction poten- tial of Ag(S:0;)}" is noble values as compared with that of Cu(S,0,)§", and the potential difference is about 0.3V. Under such con- ditions, the electrolytic silver recovery from vo, Xo 0s N N Au(S:Os)r+ e* = Aus 2:05 2 OT agtsionit's = Age 25:08" 2 Po(SiOa + 20° Po» 25:68 5 : g CHE OF so 200s 9OF Te * ore as Sor ONS, Se @Mcomptex= 5% 107 Ag. = ays = 1 1.0 5 10 15 pH Fig. 1 Potential-pH diagram for the system of M- S,0}"-H,0 at 298K. Koichi Arai, Sumiko Sanuki, Norio Minami and Satoshi Sunada the solution containing Ag(S:0;)}" and Cu($.0;)" ions is possible without the con- tamination of metallic copper. However, the reduction potential of Pb(S:03)3~ is near com- parison with that of Ag(S,0;)}", and thus it is concluded that the electrolytic silver recovery without contamination of metallic Pb from the solution containing Pb(S:03)3~ ion is difficult. On the other hand, as the cathodie potential in- creased, the following reductive reaction is con- sidered: S,O¥ig) + 8Hilg) + 87 = 2HSiq)+ 3H:0 a Exy)=0.0002—0.0147 log as- 0.0073 log as,o;-—0.0591 pH (1) Furthermore, the following oxidative reaction of thiosulfate ions is considered at the anode during the electrolysis: 28:0%iq) = SsORaay + 2€7 @ Eyy=0.219 0.0591 log as,0;- +0.0295 log as,o;- Qy S20 Gq) + SH:0 = 280%) + 10H Ga) + 8e~ (3) Eyyy=1.213+0.0148 log aso3- = 0.0074 log as.o;-—0.074 pH 3)! Therefore, the spent anolyte must be treated by a supplementary method. From the thermodynamic consideration, the proposed electrolytic silver recovery process for the oxidative leach residue of Cu-anode slime which contains more than 37 mass% Ag component and small amounts of minor con- tents of Cu, Pb and Se, is schematically shown. in Fig. 2. The process consisted of three treat- ment stages, a thiosulfate leaching of the ox- idative leach residue of Cu-anode slime, an electrolytic silver recovery from the leach solu- tion and a recovery of AgsS from the spent anolyte. ‘The chemical and the electrochemical reac- tions of the new process are summarized as follows: (1) Thiosulfate leach The thiosulfate leaching reactions for the ox- idative leach residue of Cu-anode slime are con- sidered.Silver Recovery from the Oxidative Leaching Residue of Copper Anode Slime Acton of teach 01 Teach residue anotyte [Erectratytic Ag | Recrcle of recovery © | catholyte sssition AL Precipitation a] 49 Nass 49,5 ml Seijd-Lauia Recovery Waste iquor oF Ags Fig. 2. Proposed electrolytic silver recovery process for the oxidative leaching residue of Cu-anode slime. AgCly + 28,0} )= Ag(S:03)3" + Clizq AG2s= —20.6 kJ/mol (4) Ag:0—) + 48:09) +20) =2Ag(S:0:)3" + HOw, AGSe= —224.9 kJ/mol (5) Cu:0, + 68:0 s0a)+ 2H) =2CU(S:0;)iiaa) + Hew AGS.= —148.1 kJ/mol (6) PO q+ 252075eq) + 2H “oa 'b(S:05)hiag) F HO. AG3q= 102.2 kJ/mol (7) ‘Therefore, the leaching reactions are ther- modynamically available. (2) The electrochemical reactions for the recovery of silver The electrolytic silver recovery reaction and the cathodic reactions for Cu(S:0;)j~ and Pb(S,0;)3> ions may be experessed by the eqs. (8), (9) and (10), respectively. Ag(S:05)}aq) +e” = Agyy + 28:03 (8) Cu(S.03)Saq) +” = Cu) + 38,0) eo Pb(S:03)fiaqy + 2e” =P +2S:0%%) (10) 167 From the thermodynamic consideration, it would appear that the new electrolytic silver recovery process for the oxidative leach residue of Cu-anode slime is available, and this pro- cess would eliminate an environmental prob- lem. II. Experimental 1. Materials ‘The two samples of the oxidative leaching residue of Cu-anode slime were used in this study. The chemical compositions of the samples are listed in Table 1. The main com- ponents of the samples A and B are 37 and 36.8 mass% Ag, respectively, and the small amounts of minor elements such as Pb, Cu and Se are contained in both sample. The samples were crushed and screened into —200 mesh, and the mesh fraction was used for the leaching test. By X-ray diffraction analysis of the samples, the main component is detected as AgCl. 2, Reagent All the reagents used in this study were of the guaranteed grade. Deionized water with the electric resistivity of more than 5X 10'@-m. was used for the preparation of the solution. 3. Analytical method The concentration of the components of Ag, Pb and Cu in the leaching solution and the elee- trolyte were analyzed by means of atomic ab- sorption spectrometry, and the concentration of the thiosulfate ions in the solution was deter- mined by the chemical method. ‘Table 1 Chemical compositions of the oxidative leaching residue of Cu-anode slime samples used. Chemical composition /mass% Sample —— Au A 0 BOO =! not measured