Minerals Engineering 17 (2004) 495504 This article is also available online at: www.elsevier.

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The recovery of copper, by otation, from calcium-ferrite-based slags made in continuous pilot plant smelting trials
W.J. Bruckard *, M. Somerville, F. Hao
CSIRO Division of Minerals, Box 312, Clayton South, Vic., 3169, Australia Received 23 October 2003

Abstract A series of laboratory batch otation tests was conducted on a suite of calcium-ferrite-based slags made in continuous pilot plant smelting trials. The smelting tests were conducted as part of a wider CSIRO Minerals research project aimed at developing a singlestage continuous copper making process. The slags treated included two moderately reduced low copper slags, an oxidised high copper slag and a very reduced low copper self-pulverising slag. The total copper content of the slags varied from 5.2% to 15.1% Cu. The copper was present in the form of metallic copper, oxide copper and copper ferrite phases with the dominant phase in all slags being metallic copper. The slags were crushed, ground, wet screened at 210 or 75 lm to remove coarse metallic particles of copper, and oated at natural pH (about pH 11) using reagents and conditions appropriate for the selective recovery of the copper phases. In rougherscavenger tests on the slags total copper recoveries between 80% and 87% were obtained for three of the slags tested. The best result for the fourth slag (low copper self-pulverising slag) was 74% copper recovery. Coarse copper metal was present in the otation tails for this test suggesting the pre-otation screen size was too coarse. Further optimisation of the grinding and otation conditions for this slag should yield an improved copper recovery. Minor dierences in copper/iron selectivity for the otation tests on the four slags were observed with the low copper slag giving the most selective result and the high copper slag the least selective result. These trends were generally consistent with the kinetic data obtained in the otation tests and the given copper mineralogy for the dierent slag types. Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved.
Keywords: Froth otation

1. Introduction Over the past few years CSIRO Minerals has been conducting research aimed at developing a continuous copper converting process to replace the traditional twostage batch process that is currently used to produce blister copper (Jahanshahi et al., 1994, 1995). Sirosmelt type reactors and calcium-ferrite (lime-based) slags have been used rather than the conventional iron silicate slags. A number of advantages of using calcium-ferrite slags rather than conventional iron silicate slags have been identied and are described elsewhere (Eerola et al., 1984).

* Corresponding author. Tel.: +61-3-9545-8500; fax: +61-3-95628919. E-mail address: warren.bruckard@csiro.au (W.J. Bruckard).

The research work has now been extended to focus on the development of a single-stage continuous copper making process (so-called direct copper converting) in which copper concentrates are converted to low sulphur blister copper in a single step, that is the smelting and converting steps occur in one continuous stage (Somerville et al., 1995). Preliminary kilogram-scale laboratory and pilot plant experiments have shown the smelting process is technically feasible. One feature of the direct copper converting process is that copper losses to the slag phase can be high, meaning the slag produced needs to be re-treated to recover the copper value. The feasibility of the whole copper making process will most likely depend on the eciency and cost eectiveness of the copper recovery stage. The slags produced so far in single-stage copper making laboratory studies have varied in copper content from about 3% to 20% Cu. The copper can occur in the slag as copper metal (Cu0 ), copper oxide (Cu2 O and CuO) and

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a calciumcopper ferrite phase ((Cu,Ca)O Fe2 O3 ) with the deportment of copper to each phase type being dependent on the slag chemistry. The oxidation state (Fe3 /Fe2 ratio) and the CaO/Fe ratio in the slag are the two critical smelting parameters. Both, for example, inuence the stability of the ferrite phase, which is the phase that presents the most diculty from the point of view of recovering copper. Flotation has been identied as the most economical option to recover the copper from direct copper converting slags (Somerville et al., 2000) where it has been estimated that a copper recovery from the slag of above 90% is required to make the overall single-stage copper making process economically feasible. The results of batch otation tests undertaken on a suite of slags made in laboratory smelting tests (Bruckard et al., 2003) showed that total copper recoveries above 90% could be obtained from slags where the predominant form of copper was metallic copper. To prove the smelting process at pilot plant scale approximately 850 kg of slag (three dierent slag types) was produced in CSIRO Minerals pilot scale continuous Sirosmelt reactor. Batch otation tests were then undertaken on these slags (referred to here as pilot plant slags) to conrm or otherwise the previous otation results obtained and to help identify operating conditions for any future continuous otation pilot plant trials. The results of the batch otation work undertaken on the pilot plant slags are presented in this paper.

reduced low copper self-pulverising slag, and a fourth moderately reduced low copper slag prepared from Escondida copper concentrate. A description of the slags tested together with their chemical composition (ICP analysis) is given in Table 1. The analytical results in Table 1 show that the slags tested varied in total copper content from 5.2% to 15.1% Cu with the Escondida slag having a mid-range value of 9.8% Cu. The CaO/Fe ratio was typically 0.63 except for the Escondida slag where it was 0.55. In general, the higher the copper content the more oxidised the slag. It is also noted that for all the slags at least 75% of the copper present was in the form of metallic copper. The copper-bearing and other phases present in the slags are discussed in more detail later. 2.2. Crushing and blending All the pilot plant slags, except the self-pulverising slag, were crushed before grinding. The slags were crushed to pass 2 mm using a laboratory jaw crusher in closed circuit with a screen. Coarse pieces of metallic copper were removed by hand and discarded. They were not included in metal recovery calculations. Crushed or as received samples were then blended and ried into 200 g lots for otation testing. Sub-samples were cut out for chemical and sizing analyses. The amount of tramp copper removed during crushing, expressed as a percentage of the total slag weight, was variable and ranged from 0% to 2%. It is expected that in any continuous operation this tramp copper would be readily recovered. 2.3. Grinding and screening For each test, a 200 g batch of slag (as received or crushed) was mixed with 100 ml of distilled water and ground at 67% solids by weight in a small stainless steel rod mill (13 cm by 13 cm) with fteen stainless steel rods (18 mm diameter). Grinding times were varied to achieve the desired P80 by weight for the ground products. The grind times for each slag type were established by conducting standard grindability tests. For most tests the target P80 was 40 lm. This grind size was found to be suitable in previous otation test-work on continuous converting slags (Bruckard et al., 2003). Before each grind the mill and rod charge were cleaned by grinding with quartz and distilled water for 5 min.

2. Experimental procedures 2.1. Slag samples Laboratory batch otation tests were conducted on four slag samples containing dierent levels of copper. The slags (referred to here as pilot plant slags) were made in continuous pilot plant smelting tests, conducted on-site at CSIRO Minerals using a Sirosmelt reactor and copper sulphide concentrates from MIM and Escondida. Details of the smelting trials are described by Jahanshahi et al. (1995). The slags treated included three prepared from MIM copper concentrate, namely a moderately reduced low copper slag, a more oxidised high copper slag, a very
Table 1 Description and chemical analysis of slags Slag type Very reduced low copper self-pulverising slag Moderately reduced low copper Escondida slag Moderately reduced low copper slag Oxidised high copper slag
a

Cu (%) 5.24 9.77 7.87 15.10

Cu0 (%)a 5.22 8.21 6.95 11.4

Fe (%) 33.6 34.6 34.7 32.0

Mg (%) 3.66 2.55 3.74 4.07

Ca (%) 15.2 13.6 15.8 14.2

Si (%) 7.36 8.67 7.18 6.19

CaO/Fe 0.63 0.55 0.64 0.62

Metallic copper.

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Coarse metallic copper was removed from the ground pulp prior to otation by wet screening at either 210 or 75 lm. The oversize material was removed, dried, weighed and analysed, while the undersize portion became the otation feed. The coarse metallic fractions (screen oversize) were included in the calculation of overall metal recoveries.

2.4. Flotation 2.4.1. Flotation equipment Samples were oated in a 3 dm3 modied stainless steel Denver cell in which the impeller was tted with a variable speed drive and was driven from below, to allow the whole surface of the froth to be scraped with a paddle at a constant depth and rate. The cell was tted with a rubber diaphragm, sight tube and electronic sensor for automatic detection and control of the pulp level. For both conditioning and otation the impeller speed was 1200 rpm. Air was delivered to the cell at 8 dm3 /min and pulp temperatures ranged from 18 to 22 C. Frother was added continuously during otation via a variable speed dispenser at a rate of 1 ml/min. For a slag charge of 200 g the addition of 1 ml of frother was equivalent to 12.5 g/t. The pulp pH and potential were monitored continuously during testing. The pulp potential was measured using a high-impedance, dierential voltmeter with a platinum ag electrode and a calomel reference electrode. The performance of the electrode system was checked using standard ferricferrous ion solution (Light, 1972). Measured potential values were converted to the standard hydrogen electrode (SHE) scale by the addition of 245 mV. A Radiometer glass/saturated calomel electrode was used to measure pH. Before each test the pH of the system was calibrated using standard pH 7 and pH 11 buer solutions.

2.4.3. Flotation procedures Flotation tests were conducted on the wet screen undersize portions of the ground slag pulps. Standard operating procedures (Guy, 1992) and test conditions established in previous otation work on copper slag samples (Bruckard et al., 2003) were used. In general a two-stage otation procedure was adopted. The rst stage (rougher oat) involved the addition of Na2 S 9H2 O (5 min conditioning then 5 min aeration), followed by the addition of KEX (5 min conditioning) after which otation concentrates were collected over 8 min. Rougher concentrates were generally collected after 1, 4 and 8 min otation. In the second stage (scavenger oat), more KEX collector was added, the pulp conditioned (2 min) and further concentrates collected over 8 min. Scavenger concentrates were generally collected after 2, 4 and 8 min corresponding to cumulative otation times of 10, 12, and 16 min. In some tests a second scavenger concentrate was collected (4 min) after the addition of CuSO4 5H2 O activator and further Na2 S 9H2 O and KEX. All tests were conducted at the natural pH of the respective slag mixtures, which was generally between pH 10.5 and 11.5, and a scraping rate of once every 5 s was maintained for all tests. Pulp potential was measured but not controlled and the natural Eh of the system was between 200 and 300 mV SHE. The potential decreased following the sulphide addition but returned to the air set potential after the 5 min aeration stage. The pulp volume was maintained at a preset level by small additions of distilled water. All otation products were weighed wet, to allow calculation of water recoveries, washed with alcohol, dried and prepared for analysis in a standard manner. Full details of the test conditions used are given in Table 2. 2.5. Chemical analysis of solid products Slag head samples and otation products were assayed for total copper, iron, calcium, magnesium and silica by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a standard method. A separate sodium peroxide fusion was required for the silica analysis. Metallic copper was determined separately using a brominemethanol leach procedure incorporating an ICP-AES nish. 2.6. On-line solution analysis On-line monitoring of xanthate present in the pulp solution was conducted in a number of otation tests. Filtered solution samples were collected continuously from the pulp during otation and pumped to a diode array detector, set up to measure xanthate absorbance at 301 nm. The solution samples were then recycled back to the otation cell.

2.4.2. Flotation reagents The otation collector used was a commercial potassium ethyl xanthate (KEX). A fresh batch of xanthate was prepared each day as a 0.1% w/v solution in distilled water. Laboratory grade sodium sulphide (Na2 S 9H2 O) was used as a sulphidising agent and AnalaR grade copper sulphate (CuSO4 5H2 O) used was as an activator. Both of these reagents were added as solids to the otation cell as required. The frother used was a commercial polypropylene glycol frother (Cyanamid Aerofroth 65) prepared as a 0.25% w/v solution in distilled water. The otation gas was high purity bottled air (a synthetic mixture of O2 and N2 ) and distilled water was used in all tests to maintain the cell volume.

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Table 2 Test conditions and total reagent additions for otation tests on pilot plant slags Test no. SL28 SL29 SL31 SL32 SL33 SL34
a

Slag type Self-pulverising Self-pulverising Escondida Low copper High copper High copper

Grind time (min) 10 32 22 24 24

Pre-otation screen size (lm) 210 210 75 75 75 75

P80 (lm)a 74 37 41 41 39 39

Total reagent additions (g/t) KEX 200 200 150 150 150 250 Na2 S 9H2 O 800 800 500 500 500 500 CuSO4 5H2 O 100 100

P80 of otation tail.

2.7. Sizing analyses Sizing analyses was conducted on selected slags and otation products using standard laboratory wet and dry screening methods. Where sub-sieve sizing was required a modied CSIRO cyclosizing technique was used (Kelsall et al., 1974). With this method two further size fractions (CS6 and CS7), below those obtained by conventional cyclosizing (CS1-CS5), are collected using a continuous centrifuge and a multiple decantation procedure. All size fractions were analysed by ICP-AES. In calculating elemental distributions and cut sizes in the sub-sieve sizing range a specic gravity (SG) of 4.2 was assumed for all the slags. 2.8. X-ray diraction analyses X-ray diraction (XRD) patterns were recorded on a Philips PW 1050 goniometer with a PW 1710 diraction controller using CuKa radiation. Phases present were identied by comparison of the peak positions and intensities with data published by the International Centre for Diraction Data (ICDD).

substantial and there was also a trace of delafossite (Cu2 O Fe2 O3 ). These results are generally consistent with the total copper and metallic copper analyses of the slags (see Table 1). In all the slags the major iron-bearing component was magnetite, with minor amounts of metallic iron. The magnesium occurred as a variety of magnesium and calcium/magnesium silicates, and the calcium was also present as calcium silicate phases. 3.2. Metallurgical results Flotation test conditions and reagent additions are listed in Table 2, while a summary of the metallurgical results is given in Table 3. The results refer to the combined two-stage rougherscavenger concentrate and recoveries quoted include contributions from metallic copper recovered by wet screening prior to otation. 3.2.1. Self-pulverising slag Under certain circumstances calcium-ferrite slag will self-pulverise, or disintegrate, during cooling (Inoue and Suito, 1991; Juckes, 2002). It is believed that conditions that favour self-pulverisation are a reduced slag and a CaO/SiO2 ratio close to 2. In this work the CaO/SiO2 ratio for the slags tested varied between 1.02 and 1.50 with the ratio for the self-pulverising slag being 1.35. This apparent inconsistency was not investigated further. The suitability of otation to recover copper from this type of slag was examined using the very reduced low copper self-pulverising pilot plant slag. The P80 of the self-pulverising slag as received was 74 lm. The slag was oated as received and also after grinding (in this case the P80 of the otation tail was 37 lm). The overall results for both tests (SL28 and SL29 respectively) are given in Table 3 and a recovery-time plot for test SL28 is shown in Fig. 1. The results in Fig. 1 indicate that the selectivity of copper over the gangue elements is reasonably good and the copper recovery appears not to have reached a plateau after 20 min otation. The step in the copper recovery line at 8 min is due to the addition of extra collector. Copper sulphate was added at the 16-min mark of the oat and the shape of the recovery/time plot

3. Results and discussion Test results are discussed in terms of slag mineralogy, copper recovery, selectivity over gangue elements (especially iron), reagent considerations and particle size responses. The otation response for each slag type is considered in sequence, which follows the chronological order in which the slags were produced and tested. Flotation tests have identication numbers SL28 to SL34. 3.1. XRD analyses of slags XRD analyses were conducted on all the pilot plant slags. The results show that the major copper phase present in all four slags was metallic copper (Cu0 ). In the low copper and self-pulverising slags there were minor amounts of cuprite (Cu2 O) while in the more oxidised high copper pilot plant slag the levels of cuprite were

W.J. Bruckard et al. / Minerals Engineering 17 (2004) 495504 Table 3 Metallurgical results for otation tests on pilot plant slags Test no. SL28 Slag type Self-pulverising Time (min) 20 Ab Rb Fb A R F A R F A R F A R F A R F Component (%) Cu 16.0 73.5 5.29 20.5 64.5 5.19 29.3 80.2 9.71 31.1 86.5 8.49 33.2 81.2 14.7 32.6 81.5 14.8 Fe 35.4 25.7 33.4 26.3 12.7 33.7 25.5 19.6 31.9 24.6 16.6 32.9 22.4 26.1 29.7 23.3 28.2 30.6 Mg 3.44 22.9 3.64 2.79 12.4 3.68 1.94 19.2 2.48 2.68 16.6 3.60 2.49 22.3 3.85 2.58 24.4 3.92 Ca 10.1 16.5 14.9 13.2 13.9 15.6 10.8 21.9 12.1 12.5 19.2 14.5 11.3 30.1 13.0 12.2 33.2 13.6 3.02

499

Cu enrichment ratioa

SL29

Self-pulverising

20

3.95

SL31

Escondida

16

3.02

SL32

Low copper

16

3.66

SL33

High copper

16

2.26

SL34

High copper

20

2.20

a b

Cu enrichment ratio concentrate grade (%Cu)/otation feed grade (%Cu). A, assay; R, recovery (includes contributions from otation and wet screening); F, feed (calculated).

100 Cumulative recovery (%) 90 80 70 60 50 40 30 20 10 0 0 2 4

Cu Fe Mg Ca

8 10 12 14 Flotation time (min)

16

18

20

Fig. 1. Metal recovery as a function of otation time for test SL28 (self-pulverising pilot plant slag, as received).

would seemingly indicate that this reagent has had little eect in activating further copper for otation at this stage of the oat. In the test on as received slag, without grinding (SL28), the total copper recovery was 73.5% at 16.0% Cu (total recovery is recovery by otation and also from metallic copper recovered by wet screening prior to otation). This represents an enrichment ratio for copper (ratio of concentrate copper grade to feed copper grade) of 3.02. By contrast, in the test on ground slag (SL29), the total copper recovery was 64.5% at 20.5% Cu, representing an enrichment ratio of 3.95. At rst glance this result seems unusual in that grinding was expected to liberate more copper into oatable size

ranges and yield a higher copper recovery. The nal concentrate grade was higher in the test on the ground slag and in fact at comparable copper recoveries throughout the oats the copper grade of the concentrate is always higher in the test after grinding. This suggests that in spite of the lower overall copper recovery the liberation of copper-bearing particles has improved after grinding for this slag. The copper recovery from screening was signicantly lower in the test after grinding; only 2.5% compared with 8.8% for the as received slag, reecting the ner size distribution. In addition, the total copper recovery in the otation stage decreased after grinding from 71% to 64%. These results suggest that using a ner screen in the test after grinding might have yielded a higher total copper recovery. To verify this the otation tail from test SL29 was sized and each fraction assayed. The distribution data for copper is presented graphically in Fig. 2 and this shows that two-thirds of the copper is contained in particles coarser than 32 lm and nearly one-third in particles coarser than 53 lm. The grade of the +53 lm fraction (containing 31.8% of the copper in the tail) was 16.6% Cu while the grade of the +75 lm fraction (containing 6.13% of the copper) was 29.5% Cu. Recall the grade of the combined otation (rougher/scavenger) concentrate for this test was 20.5% Cu. Combining the coarse material (+53 lm fraction) of the tail with the rougher/scavenger concentrate (in essence the equivalent to reducing the preotation screen size from 210 to 53 lm) increases the

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Copper distribution (%)

40

30

20

10

10

20

30

40

50

60

70

80

90

100

Particle size (microns)

Fig. 2. Distribution of Cu as a function of particle size in otation tail from test SL29 (self-pulverising pilot plant slag).

overall copper recovery to 75.8% at a grade of 19.8% Cu. This result is better than the overall result from SL28 (73.5% recovery at 16.0% Cu), the comparative oat on unground slag, in respect of both copper recovery and grade. While the above calculations help explain some of the dierences between the two tests on the self-pulverising slag and indicate how it might be feasible to lift total copper recovery above 75% by optimising the screen size after grinding, the more important question is why the copper liberated by grinding into a oatable size range did not oat as well as expected. Copper recoveries exceeded 90% in previous otation tests on self-pulverising slags made in laboratory smelting trials from the same feedstock (Bruckard et al., 2003). Given that 99% of the copper in the self-pulverising slag used in this work was metallic copper it follows that the copper losses in the otation tails will be predominantly metallic copper. Possible reasons for the lower recoveries obtained could include: the shape of the metallic copper particles, insucient otation time, or insucient collector or sulphidising agent. Some of these points are discussed below. Spherical prills of metallic copper would be expected to be harder or slower to oat than akes or attened copper metal particles given there is greater scope for air bubbles to make contact with akes or attened particles. Generally grinding has the eect of attening spherical copper metallics and so this explanation would seem to be at odds with the present metallurgical results. However, the grind time for the self-pulverising slag was short (10 min compared with 2232 min for the other slag types) due to the already ne size of the as received self-pulverising slag. The limited grinding may have had an impact on the extent to which any metallic prills present were attened. Some optical or SEM studies would be needed to verify shape eects in this system.

Another possibility relates to otation retention time. The shape of the recovery-time plots for both tests indicates copper recovery has not reached a plateau after 20 min. One interpretation could be that the relatively coarse metallic copper is slow oating. Insucient collector levels may be another possible reason for poor oatability of metallic copper. This possibility was investigated further by considering the collector (xanthate) level in the otation pulp as a function of otation time for both otation tests. The collector concentration/time plot for test SL28 (as received slag) is presented as Fig. 3. Reagent addition levels and times are noted on the graph. The three major peaks shown clearly in Fig. 3 after 0, 15 and 30 min relate to the three sequential collector additions of 100, 50 and 50 g/t KEX respectively. The rate of disappearance of xanthate from solution is similar after each addition and arises from a combination of collector adsorption onto mineral surfaces, decomposition or oxidation of the xanthate in solution, and dilution by makeup water added during the otation stages. The data suggests that residual xanthate levels are sufciently high to rule out the possibility that low collector levels may have adversely inuenced the copper otation performance. The small rise and fall in xanthate level at the 26-min mark is due to the addition of sodium sulphide. When the potential of the otation pulp is reduced by the addition of a reductant like sodium sulphide some xanthate from the mineral surface is released back into solution and then re-adsorbed as the potential increases when air is turned back on in the cell for otation. The xanthate concentration/time data for the otation test on ground self-pulverising slag (SL29) is not shown but is similar to that for test SL28. Only KEX collector was used in this study. Longer chain xanthates or other stronger collectors could also be considered in further work to help improve the oatability of coarse metallic copper.
500 g/t Na2S 100 g/t KEX 50 g/t KEX 300 g/t Na2S 100 g/t CuSO4 50 g/t KEX

10 KEX concentration (ppm) 9 8 7 6 5 4 3 2 1 0 0 5 10 15 20 25 Time (min) 30 35 40

Fig. 3. KEX concentration as a function of otation time for otation test SL28 (self-pulverising pilot plant slag). Note KEX additions of 100, 50, and 50 g/t made at 0, 15, and 30 min respectively. Flotation periods are 614, 1725 and 3236 min.

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3.2.2. Low copper, high copper and Escondida slags Samples of crushed Escondida, low copper and high copper pilot plant slags were each ground for dierent times to determine the grind time required to achieve a otation feed P80 of about 40 lm. Flotation tests were then conducted on each slag type (Escondida, SL31; low copper, SL32; and high copper, SL33, SL34). Table 2 lists the test conditions and reagent additions while the overall metallurgical results for each test are given in Table 3. Recovery-time plots for each oat are shown in Figs. 46 respectively. The results in Table 3 and Figs. 46 show that after 16 min otation total copper recoveries of 80.2%, 86.5% and 81.2% were obtained for the Escondida, low copper and high copper pilot plant slags respectively, at grades of 29.3%, 31.1% and 33.2% Cu. The enrichment ratios obtained for copper were 3.02, 3.66 and 2.26 respectively. The lowest enrichment values were obtained for the tests on the high copper slag. In general the selectivity of copper over the gangue elements for each slag is reasonably good and as with the tests on the selfpuverising slag the copper recovery appears not to have reached a plateau after 16 min otation in each test.
100 Cumulative recovery (%) 90 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16 18 20 Cu Fe Mg Ca

100 Cumulative recovery (%) 90 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 Flotation time (min) 16 18 20 Cu Fe Mg Ca

Fig. 6. Metal recovery as a function of otation time for test SL33 (high copper pilot plant slag).

Flotation time (min)

Fig. 4. Metal recovery as a function of otation time for test SL31 (Escondida pilot plant slag).

100 Cumulative recovery (%) 90 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 Flotation time (min) 16 18 20 Cu Fe Mg Ca

Fig. 5. Metal recovery as a function of otation time for test SL32 (low copper pilot plant slag).

Interestingly, the shape of the recovery-time plots for the Escondida and low copper slags are similar and not unlike those obtained for the tests on the self-pulverising slag. However, the shape of the high copper plot is somewhat atter. This is most likely reective of the dierent copper mineralogy for the more oxidised high copper slag. The XRD results showed this slag to be the only pilot plant slag containing appreciable levels of oxidised copper in the form of cuprite and delafossite. Previous otation work on continuous converter slags indicated that the more oxidised forms of the copper present were generally slower oating than metallic copper, at least for ne and intermediate size ranges (Unpublished CSIRO data). The result for test SL34, a repeat of the standard test on the high copper slag (SL33) using a higher initial collector addition and a longer otation time, was similar to the SL33 result. The otation tails from tests SL31 to SL33 were sized and each fraction assayed to determine the size distribution of the unoated copper. The elemental distribution data is presented in Table 4. The data in Table 4 indicates that in all three tails the distributions of calcium, iron and magnesium largely follow the weight distribution. The copper distribution for the high copper slag tail also follows the weight distribution while for the low copper and Escondida slag tails there is proportionally more copper at the coarse end. This is most likely due to the presence of coarser metallic copper in the low copper and Escondida slag tails, which has not oated. That there may be less coarse metallics in the high copper oat tail may relate to the higher levels of oxide copper (cuprite and delafossite) in this slag. Certainly the unoated copper in all three tails appears to lie in a oatable size range (<75 lm). The reasons this copper has not oated are probably the same as those posed earlier for the selfpulverising slag; namely insucient reagent dosage or otation time, or the diculty in recovering certain size or shaped copper metal particles.

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Table 4 Elemental distributions as a function of particle size for otation tails from tests on Escondida, low copper, and high copper pilot plant slags Test no. SL31 Slag type Escondida Size range (lm) +53a )53+38 )38 Total SL32 Low copper +53a )53+38 )38 Total SL33 High copper +53a )53+38 )38 Total
a

Distribution (%) Wt 7.18 16.0 76.9 100.0 6.20 17.4 76.4 100.0 4.29 17.2 78.5 100.0 Cu 10.7 20.7 68.6 100.0 12.0 26.3 61.7 100.0 4.74 16.9 78.4 100.0 Fe 7.37 16.5 76.1 100.0 6.43 18.8 74.8 100.0 4.85 18.9 76.3 100.0 Mg 7.39 16.4 76.3 100.0 6.35 18.2 75.5 100.0 4.80 18.9 76.3 100.0 Ca 6.37 14.4 79.2 100.0 5.62 14.5 79.9 100.0 3.19 13.4 83.4 100.0

This size fraction is actually )75+53 lm given the pre-otation screening stage at 75 lm.

3.3. Selectivity comparison The comparative copper otation behaviour with respect to the (pilot plant) slag type was considered in terms of the overall selectivity of copper over the main gangue element, iron, in the otation tests conducted. A selectivity plot for four of the otation tests undertaken is presented in Fig. 7. In this plot, points on a line with a slope of 1 indicate otation performance where copper and iron are recovered equally, that is, no selectivity. Plots below this line are indicative of otation where copper has been selectively recovered relative to iron. Points closest to the bottom right-hand corner indicate the most selective otation results. The selectivity results in Fig. 7 indicate no major dierences in copper/iron selectivity for the otation tests on the four slags. Overall the low copper slag gives the most selective result and the least selective result comes from the high copper slag. This is generally consistent with the kinetic data obtained in the otation tests and the given copper mineralogy for the dierent slags types. 3.4. Comparison of otation behaviour between laboratory and pilot plant slags In a previous study (Bruckard et al., 2003), batch otation tests were conducted on continuous converting slags made in batch laboratory smelting tests using copper sulphide concentrates from MIM. This copper concentrate was the same material used as feedstock for the continuous pilot plant smelting trials that produced the pilot plant slags used in the tests discussed in the present work. Given the otation test conditions used in each test program were similar, it is worthwhile comFraction of copper unfloated

1.0 No Selectivity SL33 High copper SL31 Escondida SL32 Low copper SL29 Self-pulverising

0.1 0.1 Fraction of iron unfloated

1.0

Fig. 7. Copper/iron selectivity plot for otation tests on pilot plant slags.

paring the otation behaviour between the laboratory slags and the pilot plant slags, for each slag type, produced from the MIM copper concentrate. The otation response of the laboratory and pilot plant slags by slag type is compared in Fig. 8, a grade-recovery plot for copper. Note this data represents the otation response only for each slag and any additional copper recovery by pre-otation screening is not shown on these curves. It can be seen from Fig. 8 that the copper graderecovery curves of the laboratory slags, for the three slag types considered (low copper, high copper, and selfpulverising), essentially lie on the same extrapolated lines as those for the respective pilot plant slags. There were minor dierences in the head grades of the relative slags (8.20%, 13.8% and 2.87% Cu for the low copper, high copper and self-pulverising laboratory slags respectively, and 7.87%, 15.10% and 5.24% Cu for the

W.J. Bruckard et al. / Minerals Engineering 17 (2004) 495504

100 Cumulative copper grade (%) 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 Cumulative copper recovery (%) 90 100
Low copper laboratory slag High copper laboratory slag Self-pulverising laboratory slag Self-pulverising pilot plant slag Low copper pilot plant slag High copper pilot plant slag

503

Fig. 8. Cumulative copper grade as a function of cumulative copper recovery for otation tests on laboratory and pilot plant slags.

respective pilot plant slags) and these dierences will also inuence the grade-recovery response to some extent. It is interesting to note that the low copper curves have a steeper gradient than that for the other two slags types. In spite of the similarities in the extrapolated curves, that nal copper recoveries were dierent for each comparable slag type for the laboratory and pilot plant slags suggests that further work is still needed to identify the reasons for dierences in the copper otation response that arise when the smelting step is scaled up from batch laboratory to continuous pilot plant level. On the basis of the evidence presented in this work it seems that understanding more fully the otation behaviour of metallic copper in these systems should be the focus of any such studies.

optimal. It is expected that an improved copper recovery for this slag might be possible with an extended grind time, a ner pre-otation screen size and possibly a longer oat. The scope for improving the copper recovery for the other slag types to above the target 90% mark would seem to lie in optimising the otation conditions to improve the oatability of relatively coarse metallic copper present. Minor dierences in copper/iron selectivity for the otation tests on the four slags were observed with the low copper slag giving the most selective result and the high copper slag the least selective result. These trends were generally consistent with the kinetic data obtained in the otation tests and the given copper mineralogy for the dierent slags types. The more oxidised the slag, which is normally associated with a higher total copper content, the greater the proportion of copper present as copper oxide or copper spinel/ferrite phases, rather than as metallic copper. The spinel/ ferrite phases would seem to be slower oating and given they contain both copper and iron, selective copper recovery is compromised by their presence.

Acknowledgements The authors wish to acknowledge Mr. Peter Guy and Mr. Graeme Heyes for assistance in conducting preliminary otation testing, Mr. Mick Manuele for preparing samples for analysis, the sta of the Analytical Section of CSIRO Minerals for completing the analysis of otation products, and Ms. Nicki AgronOlshina for conducting XRD analysis. Financial support for this work was provided by the Australian Government Cooperative Research Centre program through the former G.K. Williams Cooperative Research Centre for Extractive Metallurgy, a joint venture between the CSIRO Division of Minerals and The University of Melbourne Department of Chemical Engineering.

4. Conclusions A series of batch laboratory otation tests was conducted on a suite of dierent calcium-ferrite slags made in continuous pilot plant smelting trials. The slags included a moderately reduced low copper slag, a more oxidised high copper slag, a very reduced low copper self-pulverising slag, and a moderately reduced low copper Escondida slag. The slags varied in copper content from 5.2% to 15.1% Cu. The dominant form of copper in all the slags was metallic copper. A simple grinding/screening/otation procedure was used in all tests with reagent additions typically 150200 g/t KEX and 500800 g/t Na2 S 9H2 O. In rougher/scavenger otation tests on the pilot plant slags total copper recoveries between 80% and 87% were obtained for three of the slag types tested (low copper, high copper and Escondida). The best result for the forth slag (self-pulverising) was 74% copper recovery. Coarse copper metal was present in the otation tails for this test suggesting the pre-otation screen size was not

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