Hydrometallurgy 67 (2002) 63 69 www.elsevier.

com/locate/hydromet

Base metals recovery from copper smelter slag by oxidising leaching and solvent extraction
A.N. Banza a,*, E. Gock a, K. Kongolo b,c
a

Institute for Mineral Processing and Disposal Technology, Technical University of Clausthal, Walther-Nernst-Strasse 9, D-38678 Clausthal-Zellerfeld, Germany b University of Lubumbashi, Lubumbashi, D.R. Congo c Gecamines Metallurgical Research Centre, Likasi, D.R. Congo

Received 19 February 2002; received in revised form 20 August 2002; accepted 21 August 2002

Abstract Due to its amorphous structure, smelter slag cannot efficiently be leached with sulphuric acid; the formation of silica gel induces an increase of leach liquor viscosity, difficult pulp filtration and crud formation during solvent extraction. The problem was solved by leaching with sulphuric acid under hydrogen peroxide, which also performs simultaneous iron oxidation and removal. A copper smelter slag from Lubumbashi, Democratic Republic of Congo, containing 1.4% Cu, 0.7% Co, 8.9% Zn and 20.9% Fe(II), has been used in this study. The leaching tests have been carried out at normal pressure on ground slag samples ( < 100 Am). Silica gel-free solutions containing copper, cobalt and zinc were produced, so that pulp filtration could be easily carried out. The dissolved base metals were successfully extracted from solution by solvent extraction using kerosene Shellsol D70 as diluent. Copper was extracted with LIX 984 and stripped with sulphuric acid solution. Thereafter, cobalt and zinc were collectively extracted with D2EHPA and then separated by selective scrubbing with sulphuric acid solutions of different dilutions. This method provided an overall recovery of 80% Cu, 90% Co and 90% Zn in separated solutions which could be further treated by electrowinning or salt precipitation. D 2002 Elsevier Science B.V. All rights reserved.
Keywords: Copper smelter slag; Copper cobalt zinc recovery; Sulphuric acid leaching; Hydrogen peroxide; Solvent extraction

1. Introduction Various hydrometallurgical methods using lixiviants such as acids, bases and salts have been developed for base metal extraction from smelter slags. Aydogan et al. (2000) obtained more than 92% Cu from Hafik Madentepe copper slag contain*

Corresponding author. Fax: +49-5323-72-2353. E-mail address: anbanza@yahoo.com (A.N. Banza).

ing 2.62% Cu by sulphuric and ammonia leaching at 95 jC. Gbor et al. (2000) achieved 77% Co and 35% Ni from INCO nickel smelter slag containing 0.13% Co and 0.29% Ni by aqueous sulphur dioxide leaching. More than 80% of Cu and Co could be extracted from different slags by leaching with H2SO4, FeSO4, (NH4)2SO4, FeS2, NaCl or FeCl2 after roasting (Herros et al.,1998; Anand et al., 1981; Tumen and Bailey, 1994; Sukla et al., 1986). Anand et al. (1983) extracted more than 90% of Cu, Co and Ni from

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 1 3 8 - X

64

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369 Table 1 Chemical composition of the sample from the Lubumbashi copper slag dump Constituent Cu Co Zn Fe S Si Ca Mg Al

Ghatsila smelter copper slag containing 4.03% Cu, 0.48% Co and 1.98% Ni by pressure leaching at 130 jC. Information on iron coextraction and silica gel formation is missing in most of these studies. During sulphuric acid leaching of slag, silica gel is formed according to reaction (1). The presence of silica gel not only prejudices metal extraction and pulp filtration, but also causes crud formation during solvent extraction. 2FeO SiO2 2H2 SO4 ! 2FeSO4 H4 SiO4 1

Amount (%) 1.43 0.72 8.90 20.70 0.59 15.37 6.26 2.53 2.56

sulphides. Cobalt is finely disseminated in the slag matrix. Zinc is present as ferrites and silicates. 2.2. Leaching of the slag The leaching batch tests of ground slag ( < 100 Am) with a combination of H2SO4 and H2O2 (50 vol.%) were done in a 1-L round bottom glass reactor with four openings serving for a pH electrode, a condenser tube, a thermometer and a mechanical stirrer. Hydrogen peroxide was continuously added to the pulp during the leaching. The effect of leaching time, temperature, oxidant dosage and potential (Eh) has been investigated. The leach liquor and the residues were analysed for copper, cobalt, zinc and iron by AES/ICP or AAS. 2.3. Solvent extraction

Nonferrous metal extraction, iron removal and production of good filterable pulp have been performed in this study by sulphuric acid leaching in the presence of hydrogen peroxide at normal atmosphere. Sulphide and iron oxidation takes place in leaching system according to reactions (2) and (4). Dissolution of iron(II) from slag is expressed by reaction (3). CuS 2H2 SO4 2H2 O2 ! CuSO4 2H2 SO3 2H2 O FeO H2 SO4 ! FeSO4 H2 O 2FeSO4 H2 O2 2H2 O ! 2FeOOH 2H2 SO4 4 After filtration, the leach liquor was treated by solvent extraction using classic extractants such as LIX 984 for copper and D2EHPA (di-2-ethylhexyl phosphoric acid) for cobalt and zinc. 2 3

2. Experimental 2.1. Material The slag sample used in this investigation is a composite from different levels of the copper slag dump in Lubumbashi, Katanga, Democratic Republic of Congo, whose chemical composition is given in Table 1. A mineralogical study by Banza et al. (2002a,b) showed that this slag has a fayalite structure. More than 80% of copper is in the form of

Selective metal extraction from aqueous phase containing 1.99 g/L Cu2 + , 1.04 g/L Co2 + , 12.58 g/ L Zn2 + and 2.57 g/L Fe3 + from the above-described oxidising leaching was carried out in glass vessels. The extractants LIX 984 for copper and D2EHPA for zinc and cobalt were used in this investigation. Kerosene Shellsol D70 was used as diluent in both cases. These reagents were supplied by Henkel KG Duesseldorf, Germany. After copper extraction, iron was removed from solution with calcium carbonate. Cobalt and zinc were then simultaneously extracted and thereafter separated by selective stripping with sulphuric acid solution of different concentrations.

3. Results and discussion 3.1. Leaching of the slag 3.1.1. Sulphuric acid leaching of copper smelter slag Leaching tests were carried out at pH 2.5 on ground slag samples ( < 100 Am). Figs. 1 4 show

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369

65

Fig. 1. Temperature effect on copper leaching recovery (10% solid, particle size: 100% < 100 Am, pH 2.5, H2SO4 consumption: 500 kg/t slag).

Fig. 3. Temperature effect on zinc leaching recovery (10% solid, particle size: 100% < 100 Am, pH 2.5, H2SO4 consumption: 500 kg/t slag).

the reacted fraction of copper, cobalt zinc and iron during leaching in the temperature range between 24 and 80 jC. About 60 min was required to obtain high copper, cobalt and zinc extraction. Temperature increase from 24 to 60 jC significantly increased metals leaching recoveries, especially for copper. The effect of further temperature increase, from 60 to 80 jC,

was negligible in all cases. Filtration of the resulted pulp from the leaching at 24 and 60 jC was very difficult because of presence of silica gel. The silica content in the leach liquor varied between 3 and 8 g/ L depending on acid content. Best leaching results were obtained at 80 jC with metals recoveries of around 60% Cu, 90% Co, 90% Zn and 90% Fe after 2 h.

Fig. 2. Temperature effect on cobalt leaching recovery (10% solid, particle size: 100% < 100 Am, pH 2.5, H2SO4 consumption: 500 kg/t slag).

Fig. 4. Temperature effect on iron leaching recovery (10% solid, particle size: 100% < 100 Am, pH 2.5, H2SO4 consumption: 500 kg/t slag).

66

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369

3.1.2. Leaching at constant flow rate of hydrogen peroxide The H2O2 flow rate was varied from 0 to 125 L/t slag. Fig. 5 shows the metals leaching recoveries at 70 jC and pH 2.5 as a function of H2O2 consumption. Around 62.5 L/t slag was the optimal dosage of H2O2. This is higher than the stoichiometric need for oxidation of copper sulphide and ferrous iron according to reactions (2) and (4). Without adding of hydrogen peroxide, pulp filtration was difficult. H2O2 addition to the leaching system considerably decreased iron dissolution from over 90% to less than 5%, while it increased the copper recovery from 60% to 85%. Cobalt and zinc recoveries were not affected. Fig. 6 shows the metal extraction as a function of leaching time at 35 L H2O2/(ht). The Eh values measured during the leaching were 292, 358, 434, 622 and 645 mV at 15, 30 60, 90 and 120 min, respectively. Copper extraction and iron removal are proportional to H2O2 dosage in the first 2 h. Around 180 min was required to obtain the highest extraction of copper, cobalt and zinc and the lowest iron dissolution. Although the long leaching time was necessary for iron and silica gel removal, no significant increase of the base metals recoveries could be observed after 120 min. The dissolved iron quantity increased during the first 10 min, decreased strongly

Fig. 6. Kinetic of metal recovery by oxidising leaching with H2SO4 of copper slag (10% solid, particle size: 100% < 100 Am, pH 2.5, temperature: 70 jC, H2O2: 35 L/(ht)).

after 15 30 min and slowly down after around 90 min. This could be due to the solution potential Eh which was higher than 600 mV after 90 min. In fact, low potentials prevailing before this time are not suitable for iron oxidation. Ney (1973) reported that some metal oxides can modify the negative zeta potential of silica suspension. Simultaneous silica gel formation and iron removal as goethite have produced a good filterable pulp. The leach liquor at pH higher than 2 contained less than 0.5 g/L Si. In contrast to the leaching with H2SO4, no gel formation was observed after 1 year storage of leach liquor obtained with H2SO 4 H2O2 combination. Metal extractions of more than 80% Cu, 90% Co, 90% Zn and 5% Fe were recorded at 70 jC and pH 2.5. According to Dutrizac and Monhemius (1986), the goethite stability field is situated in the pH range higher than 2 and the temperature range 40 100 jC. Although higher cobalt, copper and zinc recoveries and iron removing could be obtained at pH value lower than 2, pulp filtration became difficult in this pH range. Similar results were recorded by treating the same slag material with the use of digestion method and roasting (Banza, 2001; Gock et al., 2001; Banza et al., 2002a,b). 3.1.3. Leaching at constant potential Eh The leaching tests have been conducted at pH 2.5 and 70 jC to investigate the effect of potential Eh on

Fig. 5. Metal recovery at different H2O2 dosages by oxidising leaching with H2SO4 of copper slag (10% solid, particle size: 100% < 100 Am, pH 2.5, temperature: 70 jC, leaching time: 120 min).

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369

67

Table 2 Copper extraction with LIX 984 in three stages and copper stripping with H2SO4 in three stages Element Feed (mg/L) Copper extraction (%) A/O A/O A/O A/O A/O A/O A/O 1:2 1:1 2:1 2:1 1:1 1:2 1:4 Cu 1986 98.6 99.3 99.4 99.2 99.0 98.2 98.0 Co 1030 0.76 0.81 0.72 0.79 0.80 0.76 0.78 Zn 12,578 0.48 0.62 0.58 0.59 0.52 0.54 0.46 Fe 2586 0.09 0.10 0.11 0.08 0.06 0.07 0.05

Copper stripping (%)

Fig. 7. Metal recovery as a function of potential Eh by oxidising leaching with H2SO4 of copper slag (10% solid, particle size: 100% < 100 Am, pH 2.5, temperature: 70 jC, leaching time: 180 min).

at 650 mV. At 450 mV, iron dissolution remained constant at approximately 15% independently of the leaching time. Copper dissolution significantly increased with the potential increase from 450 to 650 mV, while iron dissolution simultaneously decreased. 3.2. Metal recovery by solvent extraction

the leaching result. The potential was varied in the range 450 650 mV by H2O2 addition. Fig. 7 shows that iron was better removed at higher potential values. According to Pourbaix diagrams, oxidation of ferrous ion at 25 jC is favourable at high potentials. Fig. 8 also indicates that leaching at high potentials can reduce the leaching time: 65% copper was extracted after 180 min at 450 mV and only 60 min

3.2.1. Copper extraction Ritcey and Ashbrook (1984) have reported that the presence of both solids and colloids such as silica in solvent extraction feed to can produce stable emulsions and cruds during the mixing of organic and aqueous phases. This fact decreases mass transfer effects. Copper extraction was carried out using the solution given in Table 2 obtained under optimal oxidising leaching conditions. Rodriguez de San Miguel et al. (1997) have found the selectivity of LIX 984 as copper extractant in the pH range 0.5 2.5. Copper extraction was carried out in three stages with 12% v/v LIX 984 diluted in kerosene Shellsol D70 at 25 jC, at pH 2.5 and a phase ratio A/O of

Table 3 Cobalt zinc extraction with D2EPHA in two stages and cobalt zinc stripping with H2SO4 in three stages Element Feed (mg/L) Cobalt and zinc extraction (%) Cobalt stripping (%) Fig. 8. Copper and iron recovery as a function of leaching time by oxidising leaching with H2SO4 of copper slag (10% solid, content size: 100% < 100 Am, pH 2.5, temperature: 70 jC). Zinc stripping (%) A/O A/O A/O A/O A/O A/O A/O 1:2 1:1 2:1 1:1 1:4 1:1 1:4 Cu 3.90 Co 1010 97.4 96.1 95.8 95.0 94.4 0.91 0.65 Zn 11,800 99.7 99.8 98.8 0.09 0.07 97.5 95.4 Fe 53.8

68

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369

Fig. 9. Proposed flow sheet for the retreatment of copper smelter slag by oxidising leaching and solvent extraction.

1:1. More than 99% copper was extracted with less than 1% coextraction of cobalt, zinc and iron. Copper stripping was done in two stages at the phase ratio A/O of 1:1. 3.2.2. Zinc and cobalt extraction After copper extraction, iron was removed by precipitation in a round glass vessel at 85 jC and pH 3.5 with addition of a 300 g/L CaCO3 suspension. About 99% iron was removed with cobalt and zinc coprecipitation of around 3% and 5%, respectively. Residual iron content in solution was only 54 mg/L. Cobalt and zinc were thereafter collectively extracted in two stages using 20% v/v D2EPHA in kerosene Shellsol D70 at 25 jC, pH 3.5, and a phase ratio A/O of 1:1. Extraction and stripping results are given in Table 3. Cobalt stripping from organic phase was carried out in two stages with diluted sulphuric acid at 25 jC, pH 2.5. Afterwards, zinc was stripped at pH 1. More than 96% Co and 99% Zn were extracted.

Based on the present study a schematic flow sheet is given in Fig. 9.

4. Conclusions This study clearly demonstrates that oxidising sulphuric acid leaching under hydrogen peroxide at 70 jC and normal pressure can effectively be used to extract base metals from amorphous copper smelter slags after grinding at 100% < 100 Am. By using this method, both silica gel formation and iron coextraction are avoided. Silica gel-free solutions and good filterable cakes are obtained. Selective copper solvent extraction with LIX 984 followed by collective cobalt zinc extraction by D2EPHA with subsequent cobalt zinc separation by selective stripping were successfully performed without any crud formation. The use of an additional extractant for cobalt was not necessary by applying this method.

A.N. Banza et al. / Hydrometallurgy 67 (2002) 6369

69

Overall recoveries of approximately 80% Cu, 90% Co and 90% Zn in separate solutions were achieved by applying this process. The recovery of metals from their respective solutions can be carried out by electrowinning or salt precipitation.

Acknowledgements The authors would like to express their gratitude to Gecamines for supplying the slag sample which was used in this study. The award of a doctorate fellowship to A.N. Banza by the German Academic Exchange Service (DAAD) is gratefully acknowledged.

References
Anand, S., Das, R.P., Jena, P.K., 1981. Reduction roasting and ferric chloride leaching of copper converter slag for extracting copper, nickel and cobalt. Hydrometallurgy 7, 243 252. Anand, S., Rao, K.S., Jena, P.K., 1983. Pressure leaching of copper converter slag using dilute sulphuric acid for the extraction of cobalt, nickel and copper values. Hydrometallurgy 10, 303 312. Aydogan, A., Canbazoglu, M., Akdemir, U., 2000. Processing of Hafik Madentepper slag using conventional leaching methods. Mineral Proc. on the 21st Century. Balkema, Rotterdam, pp. 529 533. Banza, A.N., 2001. Process for the Recycling of Copper Smelter Slag from Lubumbashi/D.R. Congo Cuvillier Verlag, Goettingen, Germany ISBN 3-89873-151-0. In German. Banza, A.N., Gock, E., Kongolo, K., 2002a. Base metals recovery

from granulated copper slag by digestion method. Proceedings of the R02, 6th World Congress on Integrated Resources Management, Geneva, Switzerland, February 12 15, 2002. Paper No. 327. Banza, A.N., Gock, E., Kongolo, K., 2002b. Characterisation of the copper smelter slag from Lubumbashi for the recovery of valuable metals. Proceedings of the IXth IMPS, International Mineral Processing Symposium, Cappadocia, Turkey, September 18 20, 2002 (in press). Dutrizac, J.E., Monhemius, A.J., 1986. Iron Control in Hydrometallurgy. Ellis Horwood, New York, pp. 353 373. Gbor, P.K., Ahmed, I.B., Jia, C.Q., 2000. Behaviour of Co and Ni during aqueous sulphur dioxide leaching of nickel slag. Hydrometallurgy 57, 13 22. Gock, E., Kongolo, K., Banza, A.N., 2001. Process for the recycling of base metals from copper smelter slag. German Patent, DE 199 46 326 A 1, 2001-03-29. Herros, O., Quiroz, R., Manzano, E., Bou, C., Vinals, J., 1998. Copper extraction from reverberatory and flash furnace slag by chlorine leaching. Hydrometallurgy 49, 87 101. Ney, P., 1973. Zeta-Potential Ehe und Flotierbarkeit von Mineralien. Springer-Verlag, Wien. Ritcey, G.M., Ashbrook, A.W., 1984. Solvent Extraction. Elsevier, New York, pp. 249 261. Rodriguez de San Miguel, E., Aguir, J.C., Bernal, J.P., Ballinas, M.L., Rodriguez, M.T.J., de Gyves, J., Schimmel, K., 1997. Extraction of Cu(II), Fe(III), Ga(III), Ni(II), In(III), Co(II), Zn(II) and Pb(II) with LIX 984 dissolved in n-heptane. Hydrometallurgy 47, 19 30. Sukla, L.B., Panda, S.C., Panda, P.K., 1986. Recovery of Co, Ni and Co from converter slag through roasting with ammonium sulphate and sulphuric acid. Hydrometallurgy 16, 153 165. Tumen, F., Bailey, N.T., 1994. Recovery of metal values from cop per smelter slag by roasting with pyrite. Hydrometallurgy 44, 261 267.