27.4. THE TREATMENT OF STEEL WOOL CATHODES R.L. Paul, Council for Mineral Technology 27.1. INTRODUCTION The major elements deposited onto steel-woo! cathodes are gold, silver, and copper'»?>_ Mercury and lead, if present in the eluate, will also deposit on the steel wool!, although these elements are not present to any great extent in South African ores. The actual composition of the cathodes depends upon the relative concentrations of gold, silver, and copper in the eluate and the extent to which the metals are loaded onto the steel wool prior to stripping. Typical concentrations are: 60 to 70 per cent gold, S to 10 per cent silver, 5 to 10 per cent copper, and 10 to 25 per cent iron. After smelting, the gold content of the bullion dispatched to the Rand Re- finery should be above 80 per cent (800 fine) if the producer is to avoid the imposition of penalties by the Refinery. A further requirement of the Re- Finery is that the iron content should be below 3 per cent. The upper Limit For iron was imposed because bullion with higher velues of iron has a ten dency to spit when it is melted in the induction furnaces due to spontaneous oxidation of the iron by atmospheric oxygen. Even more serious, however, is the low solubility of iron in impure bullion (approximately § per cent), since it results in phase separation of the melt, which then forms two immiscible molten layers. This separation creates severe difficulties in sampling so that it is impossible for a representative analysis of the gold content of the bullion to be obtained. Hence, disputes between the producer and the Rand Refinery are almost inevitable. It is clear therefore that the treatment of the logded cathodes should not only raise the fineness of the bullion to a value exceeding 800, but should ensure that the residual iron from the steel-wool cathodes is reduced below 327.2. per cent. It is of interest for one to note that the low solubility of iron in impure bullion is due to the presence of the silver and copper (iron being totally immiscible with these metals?) and not to the alloying properties of gold and iron (these metals being miscible over the entire composition range?) . 27,2. TREATMENT WITH ACIDS At least four plants in South Africa, one in Australia", and one in the u.s.A.! digest the steel-wool cathodes in hot dilute mineral acids. The leach residue is filtered and simply melted in a small resistance or induc- tion furnace. The bullion from the four South African plants {viz. the Cooke and Doornkop plants at the Randfontein Gold Mine and the plants at the New Consort and Rietfontein Gold Mines) exceeds the purity requirements of the Rand Refinery, but no information is available for the purity of the bullion Produced at the American or Australian gold plants. The Kambaida plant in Australia and the New Consort and Cooke gold plants use hydrochloric acid (10 to 20 per cent) to digest of the steel wool whereas the American and Deornkop plants use sulphuric acid. The disadvantage of hydro- chloric ecid is that it can contribute indirectly to the dissolution of silver, by oxidation with ferric ions, Ferric is a strong oxidant for silver in the presence of chloride ions, (and is produced by the oxidation of ferrous ions by atmospheric oxygen) , Fecls + e+ Fe’t 4 act” but not in sulphate, Feo27.3, This loss of silver can be significant when the silver content of the cat- hodes is high (i.e. above about 40 per cent), and this is why sulphuric acid is used at the American plant, However, as the silver content is reduced, the metal becomes more noble, owing to a lowering in the activity of the silver, At the level of silver typically encountered in South Africa, the dissolution in hydrochloric acid should be very low. At ambient temperatures, the dissolution of the steel wool in hydrochloric acid is complete within 24 hours. Slightly longer times are required for dissolution in sulphuric acid’, although the duration can be significantly reduced by heating to moderate temperatures (about 60°C). The feed to the carbon-in-pulp plant at the Rietfontein Gold Mine has a very high copper content, and for some years the cathodes were very heavily loaded with copper. For the production of bullion with a fineness above 800, the cathodes were digested in hot nitric acid, which dissolved the residual steel wool and a high percentage of the silver and copper. After filtration to remove the gold powder, sodium chloride was added to the leach liquor to precipitate silver chloride, which was recovered in a second filtration step. fare had to be taken to ensure that no chloride ions were allowed to con- taminate the nitric acid since the gold would dissolve. Clearly, this pro- cedure was one that should be avoided if possible and, some years ago, another treatment was introduced, This involved washing of the loaded carbon with cold caustic cyanide to renove the copper prior to high-temperature elution of the gold, The treatment of the cathodes at the Doornkop CIP plant involves immersion of the cathode baskets in a tank filled with water to remove excess cyanide. The loaded steel wool is removed from the baskets and transferred to a rubber-lined, stainless-steel tank equipped with a mechanical agitator. The tank is filled with 35 per cent sulphuric acid, and digestion is allowed to proceed for 13 to 1 hours, The leaching of the steel wool is exothermic in the initial stages, which raises the temperature to about 45°C. After the leach, the residue is allowed to settle in the conical bottom of the leaching vessel, and the excess acid is decanted from the top. This acid 1s pumped27.4, through a filter press to recover any fine gold, and returned to a holding tank for reuse or neutralization, The remaining contents of the leaching vessel are transferred by gravity to a small pan filter covered with filter paper. The contents of the filter are dried in an oven and smelted with a smal] amount of borax as fluxing material (1 part of borax to 40 parts of dried gold fines by mass in an 80kW induction furnace. The gold content of the dried fines before smelting is reported as being higher than 90 per cent. In general, acid digestion of the loaded cathodes can be implemented rapidly and easily, and avoids the use of large quantities of fluxes during the smelting stage. The quality of the bullion is high, and the difficulties associated with iron in the bullion are avoided. It is surprising that this method is mot used more extensively. The major objection to this route is that it is difficult for one to maintain security when dealing with powdered gold, However, if the equipment is installed within the smelt-house, and the lid of the leaching vessel is equipped with a suitable locking mechanism, security should not present any great difficulty. 27.3, CATHODE SMELTING The process of smelting consists of two separate operations: calcination to oxidize the base metals and stagging to yield the bullion. 27.3.1. Calcinetion The cathodes are packed into steel trays and calcined at 600 to 700°C in @ plentiful supply of air for at least 24 hours, A plot of the free energy of formation of the oxides of gold, silver, copper, iron, and lead versus tem- perature (Figure 1) indicates that gold and silver are stable to oxidation at elevated temperatures, whereas the base metals will be converted to the oxides. Hhen calcination is complete, the cathodes will have a reddish colour (due to the presence of hematite) and will be very friable.27.5, 100 Au— Au,0, } AU AuaDs ob Ag Ag,0 | — cuo st, -100 F 2 Pb» PbO = % 200 F ta 200 -300 49) 1 500 i900 Tem / °C Figure 1. Free energy of reaction versus temperature27.6. Inspection of the calcine produced at the Kinross Gold Mine after 48 hours at 600°C revealed that oxidation of the steel wool had occurred only at the outermost layers, and that the bulk of the steel wool remained unoxidized. However, the efficiency was poor because the loaded cathodes had been packed into the trays so tightly that no air could reach the lower layers. 27.3.2. Slagging If the steel-wool cathodes have been effectively calcined, the addition of suitable fluxes to the calcine at 1200 to 130% will result in the formation of a slag containing the base-metal oxides. The slag and melt are poured into moulds, and allowed to cool. The bullion is then readily separated from the slag and should be well above 800 fineness. The precious-metal content of the slag should be low. The reactions occurring in the slag have been likened® to the acid-base reactions that take place in aqueous electrolytes. In terms of aqueous chemistry, a Lewis base is a potential donor of electrons, whereas a Lewis acid is an acceptor of electrons. These definitions of acidity and basicity apply equally well to the constituents of a siag®, although the chemical species involved in the reactions are manifestly different fron the ore familiar aqueous species. In slags consisting of molten oxides the predominant electron donor (i.e. Lewis base) Is the oxygen anion ~. Bases that supply & ions are the simple metal oxides Ca0, Naz0, MgO, CU, ete., as follows: cas ch a Pr, Examples of acids that can act as electron acceptors are oxides like Si0), 8503, POs, CO, etc., as follows si, + ahs sich,27,7. B03 + 30 +2 BO Eiliot® has recently reviewed the concept of basicity in metallurgical siags and rated a large number of oxides according to their degree of basicity. A selection of the oxides pertinent to the present study are listed in Table 1. TABLE 1. RELATIVE BASICITIES OF OXIDES Very acidic Very basic Pps BO, Si Guo Fed gd PbO Cad Nay decause of the basic nature of CuO and FeO, the fluxes used should be acidic, so that the resulting slag is acidic to neutral after reaction with the base~ wetal oxides, A simple flux like sand (Sid,) has far too high a melting point 1723) and viscosity to be considered. The addition of basic network breakers like Ca0 and NapO up to 50 per cent by mass reduce the liquidus (Figures 2 and 3) and viscosity markedly. Wonever, even a mixture of Nap0 and S10, at 50 per cent by mass (Figure 3) hes a liquidus thet is barely below the melting point of gold (1063°C). If part of the sand is replaced by fused borax (8,03), the tiquidus of the ternary system is lowered to the practical operating range of 650 to 860°C (Figure 4), and almost all fluxes for the melting of gold are based upon mixtures of sand and borax. It should be noted that borax or, more cor- rectly, sodium borax, Na0,2B,03, is not the same as fused borax, 8503). ariggs® reported that smelting at the Beisa Gold Mine was performed with a charge consisting of 1 part of calcine to 0,4 parts of borax, 0,3 parts of27.8, \ Kesm aco} b ‘ ad Cod + Lia. t 220" 0456, #1 a 5-090, +Li8 2000 pao Fdsiojece Poids 4 ty tote wes" a fasayte-cessa, cody hia feoss,oy+ 1600 | costae +458 tae, fenc5804 | Cr80ste-C2,51 FF tvigymite + Lig. 136" Er Co,Si0, + 000 + e-cainte base) £ wx: 1200 | Tide rewonatetonte (9-C08i0) fom 40] & k- 28 | orcas +00 & “igyie + wotbsorite (8-C08'0,)—_f.c2504} + [8 C 530,47 800 or Quartz + Woltastonite: pase ESO * Y-COeS — 725" "y= casi +020 Sio, * Woh veatloo, nse esa, cn Figure 2. Phase diagram Si0,~Ca0 (ref.7)27,3, 10 00 ~ A 500 fot 100 00 00h Nad | Raps faints} Seu woh To eco} 0 oo} 8 = a Ow Dm Ho si, Figure 3. Phase diagram NaQ0-Si0, (ref .7) Figure 4. Phase diagram Na,0-B,0,-Si0, (ref .7)27.10. sodium carbonate, and 0,3 parts of silice, Reference to Table II allows the concentrations of Naj0, B)03, and Sid, to be determined as 34, 32, and 34 per cent by mass respectively. The slag formed from the above fluxes has @ liquidus of approximately 700°C, and will exhibit good fluidity at the smelting temperature of 1300°C. Furthermore, the slag is strongly acidic, and will provide good partition of the base metals into the slag. TABLE 11. SODIUM OXIDE CONTENT OF VARIOUS FLUXES Flux Molecular mass Nap0, (% by mass) Nag 6 100 NapC0, 106 59 NaNO, 85 6 Na70.2B)03 201 3 S10, 60 QO The Rand Refinery, however, reported? that the bullion from Beisa contained excessively high levels of iron, which created severe difficulties in analy- sis. The most likely reason for the presence of this iron is incomplete calcination of the steel wool to Fe or Fep0,. Because the slag-forming Fluxes used at Beisa have a low oxidizing power (only the CO, liberated from ‘the NayCOy can be considered as an oxidant), almost all the metallic iron in ‘the calcine will report to the bullion, For a while the bullion produced at Kinross was also characterized by high levels of iron®, as a result of poor calcination. Clearly, the solution is either complete oxidation of the cathodes, or the addition of a suitable oxidant Like sodium nitrate to the furnace to oxidize any residual metallic iron.27.14. Hinds and Trautman! recommend that. the steel-wool cathodes should be smelted without prior calcination using a furnace charge of 1 part of loaded cathodes to 0,4 parts of borax, 0,3 parts of silica, and 0,3 parts of sodium nitrate. Upon melting, the slag is composed of Naj0, 8,05, and Sid, at concentrations of approximately 30, 35, and 37 per cent by mass respectively. The oxidizing power of the slag is derived from the liberation of oxygen from the sodium nitrate, 3 2NaNO; + Nagd + 2NO + 205 The danger associated with this approach is that silver can be oxidized under these conditions and will report to the slag phase if an excess of sodium nitrate is used. Intuitively, the most effective means for treatment of the cathodes pyro- metallurgically requires extensive and complete calcination of the cathodes to oxidize the base metals. Gold and silver are not affected by air oxida- tion, The calcine is smelted with acidic fluxes containing a small amount of sodium nitrate to ensure the partition of any unoxidized base metals into the slag. The optimum composition and mass of the fluxes in relation to the mass of calcine will vary from plant to plant, depending upon the dase-metal content of the calcine, the efficiency of calcination, and the type of fur- nace used for smelting. Inspection of the ternary-phase diagram Na0 ~ B)(05 ~ Sid, (Figure 4) reveals that the Naj0 content should be maintained above about 15 per cent by mass, the Sid, content below 40 per cent by mass, and that the remainder should consist of 80,, If the Iquidus of the slag Is to be maintained in the region 650 to 800°C, If the slag is too viscous, the NagO content should be increased by the substitution of borax for some of the silice or by the addition of sodium carbonate, However, if the slag becomes basic, as evidenced by the presence of suspended metallic oxides in the slag or excessive corrosion of the fireclay furnace liner, the slag-to-metal ratio should be increased and the acidity adjusted if necessary. The amount of sodium nitrate added to the furnace charge should be sufficient to keep the bullion free of base metals, and excessive amounts should be avoided. Fluo-27.12, spar, CaF,, may also be added if the slag is too viscous. Careful examination of the solid slag after smelting should enable a suitable combination of fluxes to be selected for the smelting operation.27.13. REFERENCES Hinds, H.L. and Trautman, L.L., Refining of precious metals cathodes. Min. Eng. (N.Y.), vol. 35, 1983. pp, 1545-1846, Potter, G.M., Some developments in gold and silver metallurgy. EXTRAC- TION METALLURGY 81. London, Institute of Mining and Metallurgy, 1981. pp.128-136. Hansen, M, and Anderko, K., Constitution of binary alloys, 2nd edition. New York, McGraw-Hill, 1958. Sceresini, 8.9.S., The design, construction, and operation of a 500 000 ‘tonnes per annum carbon-in-pulp plant at Kambalda, Western Australia. Perth, Australiasian Institute of Mining and Metallurgy, 1982. p.130. Symposium CIP Technology for Extraction of Gold, Coudurier, £., Hopkins, 9.W., and Wilkomirsky, I. Fundamentals of metallurgical processes. Oxford, Pergamon Press, 1978. pp. 183-216. Elliott, J.F. Slags for metallurgical processes". SECOND INTERNATIONAL SYMPOSTUM ON METALLURGICAL SLABS AND FLUXES. Fine, H.A. and Gaskell, R.(eds.}. New York, The Metallurgical Society of AINE, 1984, pp.45- 62. Levin, £.M., Robbins, C.R. and MeMurdie, H.F. Phase diagrams for ceramists. Ohio, The American Ceramic Society, 1964. Briggs, A.P.K, Problems encountered during the commissioning of the carbon-in-pulp plant at Beisa Mine. J.S.Afr.inst, Min, Metall., voi. 83. 1983. pp.246-253. Rand Refinery. Private communication,