Hydrometallurgy 105 (2011) 264269

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Reductive atmospheric acid leaching of West Australian smectitic nickel laterite in the presence of sulphur dioxide and copper(II)
G.K. Das , J.A.B. de Lange
CSIRO Process Science and Engineering, Parker CRC for Innovative Hydrometallurgy Solutions, Minerals Down Under Flagship, PO Box 7229, Karawara, Perth, Western Australia 6152, Australia

a r t i c l e

i n f o

a b s t r a c t
Atmospheric acid leaching of West Australian nickeliferous smectite ore was found to be much more effective in the presence of SO2 as a reductant. The rate of leaching was further catalysed by the presence of Cu(II) in solution. The effects of SO2, acid concentration, temperature, particle size and pulp density were examined to optimise the leaching parameters. In the presence of SO2, it was possible to achieve 97% nickel extraction within 10 h leaching with less than 0.1% nickel in the leach residue using 600 kg H2SO4/t of ore with 35% w/ w pulp density at 90 C. The calculated acid consumption was 540 kg/t of dry ore for obtaining N 90% nickel extraction in the presence of Cu(II) catalyst. Cobalt and manganese extractions were very rapid, with most of their extractions within half an hour in SO2H2SO4 solution. The increase of initial acid concentration, temperature and pulp density increased the metal extraction from the ore, whereas particle size had no effect on the leaching. Crown Copyright 2010 Published by Elsevier B.V. All rights reserved.

Article history: Received 16 August 2010 Received in revised form 22 October 2010 Accepted 24 October 2010 Available online 2 November 2010 Keywords: Nickel laterite Mineralogy Atmospheric leaching Sulphuric acid Sulphur dioxide Metal extraction

1. Introduction Aqueous treatment of lateritic nickel ore for the recovery of nickel and cobalt has been developed in various owsheets. The best known processes involve high pressure acid leaching (HPAL) using sulphuric acid (Das et al., 1997b; Johnson et al., 2005; Rubisov et al., 2000; Whittington and Johnson, 2005; Whittington and Muir, 2000) and ammonia plus ammonium carbonate leaching of reduced laterite ores (Caron, 1950; Panda et al., 1980). Many other approaches have also been investigated, including atmospheric acid leaching (Bykakinci and Topkaya, 2009; Luo et al., 2010; McDonald and Whittington, 2008a,b), heap leaching (Oxley et al., 2006; Purkiss, 2004), sulphuric acid pug-roasting followed by water leaching (Canterford, 1979), sulphuric acid leaching of high temperature calcined ore (Landers et al., 2009; Li et al., 2009) and dilute acid leaching of the ore roasted in a sulphur dioxideair mixture (Canterford, 1996). Other than HPAL, all approaches involve a leaching step under atmospheric conditions which determines the suitability of the process options for the treatment of laterite ores. The atmospheric acid leaching of nickel laterites has normally been investigated using sulphuric acid (McDonald and Whittington, 2008a). However, the use of hydrochloric acid (Harris et al., 2004; Hu et al., 2009) and nitric acid (Brock et al., 2010) has also been reported where the regeneration of acid from the leach/barren liquor is considered as an important step in the process.
Corresponding author. Tel.: + 61 8 9334 8933. E-mail address: Goutam.Das@csiro.au (G.K. Das).

Sulphuric acid leaching under atmospheric pressure has been reported for various limonitic and saprolitic laterite ores (McDonald and Whittington, 2008a; Neudorf and Arroyo, 2002). However, the requirement of signicant excess acid and poor nickel and cobalt extractions (4090%) do not make this approach particularly attractive. It has been reported that the addition of a reducing agent such as sulphur dioxide (SO2) facilitates the acid dissolution of laterite ore giving high recovery of nickel and cobalt (Das et al., 1997a; Kittelty, 2008). Leaching of various iron oxide minerals such as goethite, magnetite and hematite has also been reported in several studies using different mineral acids in the presence and absence of sulphur dioxide (Byerley et al., 1979; Kumar et al., 1993; Petrie, 1995; Senanayake and Das, 2004; Surana and Warren, 1969; Warren and Hay, 1975). The acid dissolution of iron oxides in SO2 may be represented by the following equations: FeOOHs 0:5SO2 0:5H2 SO4 FeSO4 H2 O FeOOHs SO2 H2 SO4 FeSO4 0:5H2 S2 O6 H2 O Fe3 O4 s SO2 2H2 SO4 3FeSO4 H2 O Fe3 O4 s 2SO2 3H2 SO4 3FeSO4 H2 S2 O6 2H2 O H2 S2 O6 H2 SO4 SO2 1 2 3 4 5

0304-386X/$ see front matter. Crown Copyright 2010 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2010.10.016

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The rate of iron oxide leaching has been reported to be dependent on hydrogen ion concentration and SO2 concentration (Byerley et al., 1979; Senanayake and Das, 2004). Byerley et al. (1979) indicated the formation of dithionate is likely during SO2 dissolution of magnetite, whereas Das et al. (1996) identied the dithionate species in the SO2 leach solution of limonitic nickel laterite. The presence of Cu(II) in SO2 leaching of iron oxide/laterite was reported to have positive effect on the rate of leaching due to its catalytic behaviour (Byerley et al., 1979; Das et al., 1997a; Warren and Hay, 1975). The electrochemical leaching of saprolitic and limonitic nickel laterites has also been reported in the presence of SO2 to improve the nickel dissolution (Lee et al., 2005). In the previous investigations, the reductive leaching of nickel laterite with SO2 has mainly focussed on goethite-rich limonitic ores of different origin. Information relating to acid leaching performance of nickel-containing smectite ores using SO2 is not available in the literature. In this work, a typical lateritic smectite ore from Western Australia (WA) has been used for reductive acid leaching studies in the presence of gaseous SO2 at atmospheric pressure. The ore has been characterised by mineralogical analysis and leaching studies have been conducted to understand the effects of various leaching parametersacid concentration, temperature, particle size and pulp density. 2. Experimental 2.1. Sample and sample preparation The ore sample was taken from the smectite zone of an arid-region laterite deposit in WA. Initially the ore was air dried for 48 h to reduce the moisture content and to facilitate dry sample preparation. The air dried ore was jaw crushed, roll-milled and sieved to 0.106 mm. Oversize material was pulverised and added to the undersize fraction. The sample was homogenised and stored in an airtight bag after removing a sub-sample for moisture determination, chemical analysis and mineralogical characterization. 2.2. Instrumental methods and mineralogical analysis An X-ray diffractogram (XRD) was taken to perform quantitative mineralogical analysis of the sample using 10% w/w calcium uoride added as an internal standard, after mixing and ball-milling to ensure homogeneity. A Phillips Automatic Powder Diffractometer model XPERT-ARD was used to acquire the XRD traces in the range of 390 2 at a scanning rate of 1 per minute using Co K radiation. QXRD analysis was performed using Brker Advanced X-Ray Solutions TOPAS software and a set of veried crystallographic models; this includes an hkl phase derived for nontronite using a method described elsewhere (Scarlett and Madsen, 2006). 2.3. Leaching procedure The standard experimental conditions used in this study were: pulp density 20% w/w, temperature 90 C, agitation ~ 500 rpm, retention time 10 h and SO2 gas ow rate ~ 0.45 L/min. Leaching experiments were carried out in a 2 L capacity continuously stirred bafed glass reactor tted with a at ange/multi-socket lid, with the sockets being tted with quick-t glass adaptors and a condenser to prevent evaporation loss. The reactor was heated in an oil bath (UltraPeg 300) with provision to control the bath temperature maintaining the reactor temperature with 1 C. The reaction was carried out by employing SO2 gas in H2SO4 solution. Excess SO2 gas from the reactor was scrubbed in caustic solution. The required amount of de-ionised (DI) water and sulphuric acid were transferred to the reactor and placed in the oil bath. Once the test temperature was reached, a calculated amount of dry ore was

added into the reactor. The addition of SO2 gas was commenced immediately after ore addition at a continuous ow rate of ~0.45 L/min. Samples were collected at regular time intervals and ltered immediately. The solids were washed thoroughly and dried at 70 C. Both solids and liquors were analysed for Ni, Co, Fe, Mg, Al, Cr and Mn by ICP-OES. Solids were fused with Sigma 12.22 lithium borate ux and dissolved in DI water prior to ICP-OES analysis. The preliminary leaching of the ore (0.106 mm) was carried out at 90 C using 20% w/w pulp density for 10 h duration in i) SO2, ii) H2SO4 and iii) SO2H2SO4 solutions to compare the effect of SO2 on the leaching behaviour of the smectite ore. The amount of H2SO4 added in these tests was 600 kg/t of dry ore where required. The effect of temperature in this investigation was studied using 600 kg H2SO4/t of ore at 80 C, 90 C and 95 C keeping all other conditions constant. 3. Results and discussion 3.1. Chemical and mineralogical analyses The chemical and mineralogical analyses of the ore are given in Table 1. The ore contained mainly smectite (e.g. nontronite) with some serpentine (e.g. lizardite) minerals. Analysis suggests some unaccounted minerals that may be represented as amorphous silica and/or smectites. The other, minor mineral phases include maghemite/magnetite, hematite and clinochlore. The ore has moderate magnesium content (~7.8%) due to the presence of serpentine minerals and clinochlore. The smectite minerals present in the ore are likely to be iron-rich nontronites (Newman, 1987) which correlates with the iron content of the ore. It is expected also that the nickel present in the ore is mostly in the smectite minerals. 3.2. Preliminary leaching of smectite ore 3.2.1. Extraction of nickel and iron Fig. 1 shows that the leaching of the ore in SO2 solution (SO2 in water or H2SO3) was insignicant giving poor extractions of nickel and iron, whereas, with H2SO4, the extractions were ~ 74% nickel and ~47% iron after 10 h. However, in SO2H2SO4 solution, the extractions of nickel and iron were increased signicantly giving 90% and 73% respectively. Das et al. (1997a) reported a similar effect for the SO2 in H2SO4 leaching of WA limonite ore. The higher extraction of iron from smectite ore in SO2H2SO4 appears to be due to the SO2, facilitating the reduction of Fe(III)-sites within the nontronite and at the surface of the iron oxide mineral enabling Fe(II) to dissolve readily, the latter proposed previously by Byerley et al. (1979). In this process, the nickel associated in nontronite matrix dissolved with the iron (Fig. 1), as the Fe/Ni ratio was found very similar (11.311.7) after an initial 1 h of reaction. The oxidationreduction potential (ORP, with respect to Ag/AgCl reference electrode) of the nal leach slurry at 23 C was ~200 mV, 910 mV and 381 mV for the SO2, H2SO4 and SO2H2SO4

Table 1 Chemical and mineralogical analyses of the WA smectite ore. Chemical and mineralogical analyses Elements Ni Co Al Mg Fe Cr Mn Si
a

% 1.1 0.03 2.1 7.8 17.1 0.52 0.23 19.4

Mineral phases Smectitea Lizardite/antigoritea Clinochlorea Hematite Maghemite/magnetite Unaccounted Total

Chemical formula Mg0.2(Fe1.2 Mg0.5Ni0.1Al0.3) (Si3.8Al0.2)O10(OH)2.2H2O Mg2.2Fe0.2Si2O5(OH)4 (Mg10.6Al) Fe0.4(Si6.7Al1.3) O20(OH)16 -Fe2O3 -Fe2O3/Fe3O4

% 59.9 11.3 2.0 5.5 6.8 13.8 99.3

Empirical formula.

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100 90

% Ni & Fe Extraction

80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12

is highly refractory to H2SO4 leaching and partly amenable to leaching in SO2H2SO4 solution since the peak height decreased as shown in Fig 2(d). The maghemite/magnetite minerals in general are refractive to normal atmospheric acid leaching (Luo et al., 2010) but leach slowly under reducing conditions in the presence of mineral acid. The earlier work of Das et al. (1997a),b) also conrmed that magnetite present in limonite ore behaved similarly during SO2H2SO4 leaching. The hematite phase remained virtually un-affected; this explains that the rate of hematite dissolution is much slower than maghemite/ magnetite during reductive SO2 leaching with mineral acid. 3.2.2. Extraction of cobalt and manganese The extractions of cobalt and manganese in the preliminary leaching tests with i) SO2, ii) H2SO4 and iii) SO2H2SO4 solutions are given in Fig. 3 which shows that cobalt extractions are similar to that of manganese. This suggests a high correlation of cobalt association with manganese(III)/(IV) minerals in the ore. It is well known that SO2 is a suitable reagent for the leaching of manganese oxide minerals of higher oxidation states such as MnO2, MnOOH, etc. (Das et al., 2000; Kanungo and Das, 1988; Petrie, 1995). However, the extraction of manganese with SO2 in water was only ~68% after 10 h, possibly indicating that the un-leached manganese oxide is highly crystalline or that some of the manganese contained within the structure of the clay minerals and requires mineral acid for dissolution under reducing conditions. Fig. 3 shows that most of the cobalt and manganese are leached (~80%) within half an hour with a nal extraction of 95% in SO2H2SO4 solution. The kinetics of cobalt and manganese dissolution were fast in SO2H2SO4 solution compared to nickel and iron dissolution from the smectite mineral of the ore (Fig. 1). The preliminary test results clearly indicate that the impact of SO2 was signicant in the atmospheric acid leaching of the smectite ore. Therefore, the effect of a Cu(II) catalyst and various leaching parameters such as acid concentration, temperature, particle size and pulp density are discussed in the following sections to determine an optimised leaching condition. 3.3. Effect of Cu(II) catalyst The catalytic effect of Cu(II) was reported in earlier studies of the reductive leaching of iron oxide minerals and limonite ore in SO2

Time, hour
SO2 (Ni) SO2 (Fe) H2SO4 (Ni) H2SO4 (Fe) SO2 + H2SO4 (Ni) SO2 + H2SO4 (Fe)

Fig. 1. Extractions of nickel and iron during the leaching of smectite ore in SO2, H2SO4 and SO2H2SO4 solutions at 90 C using 600 kg H2SO4/t of ore, 20% w/w pulp density and 0.45 L/min of SO2.

leaching, respectively. The measured ORP using a combination of platinum/reference electrode represents the Fe(III)/Fe(II) redox couple in solution. The enhanced leaching of smectite with SO2H2SO4 produced Fe(II) which lowered the measured values of ORP. The XRD traces of the smectite ore and the nal leach residues for the previously discussed tests are shown in Fig. 2 for comparison. The residue obtained from SO2 leaching was almost identical to the feed ore, indicating that SO2 (or H2SO3) alone does not signicantly leach the smectite ore. The H2SO4 leach residue showed signicant reduction of the nontronite peak; however, a residual amount of the nontronite phase remained un-affected as indicated in Fig. 2(c) with a dotted circle. This indicates that either the remaining fraction of nontronite is difcult to leach in H2SO4 solution or the added acid was not enough to leach it completely. The leach residue from SO2H2SO4 leaching showed that the nontronite peak was almost disappeared which also correlated with the highest extraction of nickel (~90%). The ore also contained a typical serpentine mineral (lizardite) which

Fig. 2. XRD of a) smectite ore and leach residues on leaching with b) SO2, c) H2SO4 and d) SO2H2SO4 solutions. (N = nontronite, L = lizardite, C = clinochlore, M = maghemite/magnetite, H = hematite).

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267

100 90

300
Cu(II) - 0 g/L

% Co & Mn Extraction

80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12

250 200 150 100 50 0 0 1 2 3 4 5 6 7 8

Cu(II) - 1 g/L

ORP, mV

10

11

Time, hour
Fig. 4. Slurry ORP (measured at room temperature) during the leaching of smectite ore in the absence and presence of Cu(II) with SO2 using standard experimental conditions.

Time, hour
SO2 (Co) SO2 (Mn) H2SO4 (Co) H2SO4 (Mn) SO2 + H2SO4 (Co) SO2 + H2SO4 (Mn)

Fig. 3. Extractions of cobalt and manganese during the leaching of smectite ore in SO2, H2SO4 and SO2H2SO4 solutions at 90 C using 600 kg H2SO4/t of ore, 20% w/w pulp density and 0.45 L/min of SO2.

solution (Byerley et al., 1979; Das et al., 1997a; Warren and Hay, 1975). In this study, the effect of Cu(II) was investigated by adding CuSO4 in the absence of H2SO4 using standard experimental conditions. Table 2 shows that 1 g/L of Cu(II) gave a signicant improvement in metals extraction from the smectite ore. The ORP of the slurry measured at room temperature showed a considerable decrease in redox potential in the presence of Cu(II) (Fig. 4). Byerley et al. (1979) proposed that the Cu(II) catalysed mechanism for magnetite leaching proceeded through the formation of Cu(I) species in SO2 solution which reacts with surface Fe(III)-sites, reducing Fe(III) to Fe(II) and promoting dissolution; the regeneration of Cu(I) from Cu(II) occurs through an electron transfer process involving an innersphere mechanism. The standard reduction potential of Cu(II) to Cu(I) is 153 mV. Therefore, the formation of Cu(I) species in this study is supported by the decrease of ORP in the slurry from ~200 mV to 125 mV and its reaction with the Fe(III) in the smectite clay resulted in higher Fe dissolution. As the iron was leached out from smectite ore; magnesium, nickel and other elements associated with the smectite matrix were simultaneously released. However, in the following sections particular emphasis has been devoted to the extraction of nickel which is the main interest of this investigation. 3.4. Effect of acid concentration The effect of initial acid addition in this study was examined at 400 kg/t, 500 kg/t and 600 kg/t of ore, both with and without Cu(II) using standard experimental conditions. Generally, an increase in acid addition for atmospheric leaching increases the metal extractions from laterite ores (Bykakinci and Topkaya, 2009). Therefore, it was intended to keep the acid addition as low as 400 kg/t of ore, which is
Table 2 Effect of Cu(II) on metals extraction from smectite ore. Cu(II) g/L % Extraction Ni 0.0 1.0 16.1 23.6 Co 59.6 75.4 Mg 12.5 26.0 Fe 10.1 22.4 Mn 67.9 81.7

similar to the feed acid requirement of the HPAL process treating clay based arid-region laterite ores (Johnson et al., 2005). Fig. 5 shows that nickel extraction increased from 77% to 93% with an increase in acid addition from 400 to 600 kg/t of ore in the presence of SO2 and 1 g/L Cu(II). The rate of initial nickel dissolution increased with increased initial acid concentration. However, after the rst hour, the rate of reaction was similar for all the three acid additions. The dissolution rates for iron and magnesium were also similar to that for nickel. The extraction of metals at three different initial acid additions in the presence and absence of Cu(II) after 10 h are given in Table 3. The data show that the acid required to achieve above 90% nickel extraction in the reductive leaching of the smectite ore is 600 kg/t. The minimum feed acid requirement for the atmospheric acid leaching of smectitic ore of Western Turkey was reported to be N950 kg/t of ore to achieve N90% nickel extraction with a net acid consumption of 669 kg/t of dry ore (Bykakinci and Topkaya, 2009). Table 3 shows that there is an increase of nickel and iron extractions from the smectite ore leaching due to the presence of Cu(II), however, this effect is not as signicant as reported for limonite leaching, where the extractions had been reported ~25% higher for nickel and 3035% higher for iron (Das et al., 1997a). The nal free acid concentration in the leach liquor was ~ 11 g/L after 10 h of reductive leaching when 600 kg H2SO4/t of ore was used in the presence of Cu(II) giving an acid consumption of 540 kg/t of dry ore for the WA smectite. Variation of

100 90 80

% Ni Extraction

70 60 50 40 30 20 10 0 0 2 4 6 8 10 12
400 kg/t 500 kg/t 600 kg/t

Time, hour
Fig. 5. Effect of acid concentration on the extraction of nickel from smectite ore in the presence of 1 g/L Cu(II) with SO2 using standard leaching conditions.

Test conditions: Pulp density 25% w/w, Time 10 h, Temp. 90 C and SO2 ow rate ~ 0.45 L/min.

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G.K. Das, J.A.B. de Lange / Hydrometallurgy 105 (2011) 264269 Table 4 Effect of particle sizes on metals extraction from smectite ore. Particle size mm 0.106 0.425 0.710 1.200 % Extraction Ni 89.7 89.6 89.5 90.5 Co 95.0 95.1 96.8 93.8 Al 85.2 83.8 86.0 85.1 Mg 63.0 62.7 63.7 64.5 Fe 72.5 73.3 73.8 72.6 Cr 26.0 24.9 26.5 25.8 Mn 95.0 95.2 95.2 94.7

Table 3 Effect of H2SO4 concentration on metals extraction in the presence and absence of Cu(II). H2SO4 kg/t ore 400 400 500 500 600 600 Cu(II) g/L % Extraction Ni 0 1 0 1 0 1 71.7 77.4 81.9 86.8 89.7 92.8 Co 91.6 94.9 93.2 97.3 95.0 96.7 Al 56.0 63.2 73.5 80.0 85.2 89.3 Mg 51.2 52.6 56.7 58.6 63.0 66.6 Fe 54.2 68.8 65.4 77.6 72.5 83.6 Cr 19.2 21.2 23.0 26.5 26.0 29.2 Mn 91.6 96.0 93.7 96.7 95.0 95.5

Test conditions: Pulp density 25% w/w, H2SO4 600 kg/t, Time 10 h, Temp. 90 C and SO2 ow rate ~ 0.45 L/min.

Test conditions: Pulp density 25% w/w, Time 10 h, Temp. 90 C and SO2 ow rate ~ 0.45 L/min.

sized smectite ore is suitable for the SO2H2SO4 leaching route; this should reduce the cost of ore grinding. acid addition has little effect on the cobalt and manganese extractions in the presence and absence of Cu(II) as most of these metals were extracted within half an hour. 3.5. Effect of temperature The extraction of nickel increased with increasing temperature between 80 C and 95 C (Fig. 6). The initial rates of nickel extraction increased signicantly within the rst 30 min in this temperature range. The overall nickel extractions after 10 h of leaching were 85.6%, 89.2% and 91.0% for temperatures 80 C, 90 C and 95 C, respectively. The behaviour of the iron and magnesium extractions was similar to that of nickel with overall extractions of 7276% for iron and 6270% for magnesium. 3.6. Effect of particle size The effect of ore particle size was studied using four different size fractions: 100% passing through 0.106 mm, 0.425 mm, 0.71 mm and 1.2 mm, all under standard leaching conditions and using 600 kg H2SO4/t of ore in the absence of Cu(II). Variation in the particle size did not have a notable effect on the metal extractions from the ore (Table 4) giving almost identical leaching kinetics. The extractions of Ni, Fe, Mg, Al and Cr were obtained approximately 90%, 73%, 63%, 85% and 26% respectively from all the size fractions. A similar effect of particle size was reported by Bykakinci and Topkaya (2009) for atmospheric acid leaching of smectitic and limonitic laterites from Western Turkey. This indicates that a larger 3.7. Effect of pulp density The effect of solids loading upon metal extractions was studied using 20%, 25%, 30% and 35% w/w pulp densities. These experiments were performed at 90 C adding 600 kg H2SO4/t of ore, in the presence of Cu(II) and using 0.45 L/min SO2 ow rate. The results given in Fig. 7 show that extraction of nickel, aluminium and magnesium increased, whereas the iron and chromium extractions decreased, with increasing pulp density. The increase of nickel extraction was not large though; ~97% nickel was extracted at 35% w/w pulp density. The extractions of cobalt and manganese were again found to mostly occur within half an hour at all the pulp densities, giving nal extractions of ~9597%. In this study, a higher pulp density improved the extraction of the valuable metals, nickel and cobalt. The increase in pulp density meant that the initial acid concentration in the liquor also increased, as the acid to ore ratio was same in all experiments (600 kg/t of ore). This produced stronger acid leaching conditions in a reductive environment causing the smectite clay minerals in particular to dissolve at an increased rate. This was also supported by the decrease in the residue nickel content with increasing pulp density (Table 5). However, further quantitative characterization of the leach residues is required to examine the nickel distribution in the various residual mineral phases. The decrease in iron and chromium extractions was presumably due to an increase of the unleached maghemite/magnetite and chromite fractions in the leach residue. These fractions are difcult to leach, as noted for the maghemite/magnetite fraction in Fig. 2. Even under HPAL conditions, maghemite/magnetite and chromite phases are also reported as difcult phase to leach completely (Liu et al., 2010; Whittington et al., 2003).

100 90 80 100 90

% Ni Extraction

70 60 50 40 30 20 10 0 0 2 4 6 8 10 12
80C 90C 95C

% Metal Extraction

80 70 60 50 40 30 15 20 25 30 35
Ni Co Al Mg Fe Cr

40

Pulp Density, % (w/w)

Fig. 7. Effect of pulp density on metal extractions from smectite ore using the following leaching conditions: 90 C, 600 kg H2SO4/t of ore, 1 g/L Cu(II), ~ 0.45 L/min SO2 and 10 h retention time.

Time, hour
Fig. 6. Effect of temperature on nickel extraction from smectite ore using standard leaching conditions with 600 kg H2SO4/t of ore.

G.K. Das, J.A.B. de Lange / Hydrometallurgy 105 (2011) 264269 Table 5 Leach residues analyses for smectite ore leached at increasing pulp density. Pulp density% w/w 20 25 30 35 Residue analysis% Ni 0.14 0.11 0.09 0.07

269

Test conditions: H2SO4 600 kg/t, Time 10 h, Temp. 90 C, SO2 ow rate ~ 0.45 L/min, Cu(II) 1 g/L.

4. Conclusions Atmospheric acid leaching of WA nickeliferous smectite ore was found to be much more effective in the presence of SO2 as a reductant. The dissolution of the smectite ore, which mainly contained iron-rich nontronite, was facilitated in the presence of SO2 via the reduction of Fe(III)-sites within the nontronite structure. The extraction of nickel and iron were 90% and 73%, respectively, in SO2H2SO4 solution compared to 74% nickel and 47% iron when only H2SO4 is used. The rate of leaching was further catalysed by the presence of Cu(II), however, its effect was reduced with increasing acid concentration. Cobalt and manganese extractions were very rapid in SO2H2SO4 solution and N80% extractions were obtained within half an hour of reaction. The variation of initial acid addition, temperature and pulp density increased the metal extractions from the smectite ore, whereas particle size variation did not have any effect. A minimum of 600 kg/t of ore acid addition was required to achieve N90% nickel extraction during reductive SO2 leaching with 1 g/L Cu(II) at 90 C, giving an acid consumption of 540 kg/t of dry ore. An increase in the pulp density up to 35% gave a maximum nickel extraction (97%) with minimum nickel in the residue (b0.1%). Acknowledgements The authors are thankful to Milan Chovancek and his analytical team (Tuyen Phan, Bruno Latella and Elsayed Oraby Abdalla) for performing the chemical analyses and Ian Davies for the XRD data. The authors also wish to thank Robbie McDonald and Matthew Jeffrey for useful comments on this manuscript. The support of the CSIRO Minerals Down Under National Research Flagship and the Parker CRC for Innovative Hydrometallurgy Solutions are gratefully acknowledged. References
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