Minerals Engineering 24 (2011) 11881197

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Minerals Engineering
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High pressure acid leaching of a refractory lateritic nickel ore

S. Kaya, Y.A. Topkaya
Department of Metallurgical and Materials Engineering, Middle East Technical University (METU), 06531 Ankara, Turkey

a r t i c l e

i n f o

a b s t r a c t
This paper describes the experimental ndings of the extraction of nickel and cobalt by high pressure acid leaching (HPAL) of a refractory limonitic nickel laterite ore from the Grdes region of Manisa in Turkey. By optimizing the basic HPAL process parameters: leaching at 255 C with 0.30 sulfuric acid to ore weight ratio with a particle size of 100% 850l for 1 h of leaching, it was found that 87.3% of nickel and 88.8% of cobalt present in the ore could be extracted into the pregnant leach solution (PLS). However, these extraction results were found to be relatively low compared with other similar studies. In order to understand the possible reasons for this relatively lower extraction, further investigations have shown that together with a problem related to the kinetics of the dissolution reactions, a persistent acid resistant refractory mineral present in this sample also limited the leaching process. Attempts were made with different additives to solve this problem. The effects of chemical additives such as HCl, Na2SO4, FeSO4, Cu+ and sulfur were tested and the effect of each addition on the degree of extraction of nickel and cobalt was determined. 2011 Elsevier Ltd. All rights reserved.

Article history: Available online 2 June 2011 Keywords: Hydrometallurgy Laterite Leaching Nickel Cobalt

1. Introduction Ferrous and non-ferrous alloying industries, petro-chemical works, aerospace applications, nickel based catalysts and battery production, military applications, coinage and coating practices are some of the most common areas of nickel utilization in industry which lead to a high demand for this metal throughout the world. When the trends in this demand are investigated from 1950 to 2009, it is clearly seen that the need for nickel has risen from below 200 ktpa to over 1300 ktpa, and this dramatic increase is growing at an average rate of 4% per annum (INSG, 2010; McDonald and Whittington, 2008). Until recently this high demand for nickel has been supplied mostly from the sulde based nickel reserves; however, this trend is changing towards the more abundant lateritic type nickel resources, which account for about 70% of the world nickel reserves. This is due to technical, economic and environmental reasons (Moskalyk and Alfantazi, 2002). To illustrate, apart from the predominance of lateritic deposits over suldes, their easier mining by simple open-pit mining methods, unlike the extremely expensive underground mining of suldes, makes their utilization more preferable. Finally, signicant amounts of cobalt contained in laterites makes them more competitive in the nickel industry. According to annual data of nickel production from suldes and laterites, less than 10% of nickel was produced from lateritic

Corresponding author. Tel.: +90 312 2102538; fax: +90 312 2102518.
E-mail address: topkaya@metu.edu.tr (Y.A. Topkaya). 0892-6875/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2011.05.004

sources in 1950. However, this ratio increased up to 42% in 2003, and is expected to rise to 51% by 2012 (Dalvi et al., 2004; Sudol, 2005). In the light of this historical data and the changing trend towards the lateritic type nickel deposits; technically, economically and environmentally feasible processing techniques are steadily gaining more and more importance. Understanding the history of formation of a mineral deposit is critical in establishing a possible processing route for that value. Typically, the lateritic nickel ores vary widely in their chemical composition and mineralogical structure when their history of formation is considered. Depending on their lateritization history, different lateritic proles may form on a single deposit having different mineralogical formations and distribution. The zones in a typical lateritic ore are classied and named as limonitic, transition (nontronitic) or saprolitic according to their mineral content (Canterford, 1978). Naturally, the response of a specic ore to metallurgical treatment depends on the chemical composition and mineralogical characteristics of that ore. Three metallurgical extraction processes are currently being applied; pyrometallurgical, hydrometallurgical and the Caron Process. Roughly speaking, the energy intensive pyrometallurgical method generally uses the ferro-nickel production route or matte smelting process in order to recover the nickel mostly contained in the saprolitic part of the lateritic ore. However, the hydrometallurgical methods generally exploit the highly selective dissolution features of both nickel and cobalt in the limonitic and nontronitic parts of the laterite ore in sulfuric acid media. The Caron Process uses the pyrometallurgical and hydrometallurgical methods together in order to obtain the metallic values (Moyes, 2010).

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In this study, the response of limonitic nickel laterite ore from the Manisa/Grdes region of Turkey to sulfuric acid was investigated under high temperature and high pressure hydrometallurgical techniques, and the most cost effective process parameters such as leaching temperature and duration, sulfuric acid/ore ratio and particle size were examined in order to add value to this deposit. Moreover, attempts to solve the problems experienced due to low nickel and cobalt extraction were made by using suitable chemical additives. 2. Experimental 2.1. Material characterization In order to determine the general characteristics of the lateritic sample, physical, chemical and mineralogical characterization steps were performed. For this purpose, the ore was sampled by coning and quartering. Initially bulk and solid density measurements were conducted on the representative limonitic nickel laterite ore sample. Bulk density measurements were done according to the ratio of ore weight to ore volume, without joggle. On the other hand, the solid density of the sample was determined by a bottle pycnometer. After the density measurements, the moisture content determination of the as-received ore was determined by weighing and drying a representative limonitic sample in a drying oven at 105 C until a constant dry mass was attained. The limonitic sample was dried and ground to 100% 38l and analyzed chemically by the Inductively Coupled Plasma (ICP) method. Chemical analyses of the pregnant leach solutions after the leaching experiments were conducted using AAS, while the dried and ground solid leach residues were mainly analyzed by using a Niton X-Met 820 X-ray Fluorescence (XRF) analyzer and by Atomic Absorption Spectroscopy (AAS) together. In order to determine the types of minerals present in the ore samples, a Rigaku D/MAX2200/PC model X-ray Diffractometer with a Cu-Ka Xray tube working under 40 kV and 40 mA was used during the mineralogical analysis of the limonitic nickel laterite sample. Also the mineralogical analysis results were veried by the aid of a Nova Nanosem 430 Scanning Electron Microscope (SEM). Investigation of the thermal behavior of the minerals present in the limonitic nickel laterite sample was the last step in the mineralogical characterization study. For this purpose, the ore samples were dried and ground to a size of 100% 38l and subjected to Differential Thermal Analysis (DTA) and Thermo Gravimetric Analysis (TGA) by a Simultaneous Setaram DTA and TGA device. These analyses were conducted at a heating rate of 10 C/min within the temperature range of 351000 C in air in an alumina crucible. 2.2. Experimental set-up and procedure

ceed until the target leaching duration was attained. After the required leaching duration was completed, the system was allowed to cool to room temperature for approximately 1 h, by means of water owing through a titanium cooling coil. In order to perform solid/liquid separation after leaching, the resultant slurry was ltered by the aid of a vacuum pump and Whatman grade-40 lter paper on a Buchner funnel. After loading the pregnant leach solution with leached metal cations, the solid that remained in the Buchner funnel was washed well in order to completely remove the pregnant leach solution. The resultant leach residue was then dried overnight at 105 C ready for chemical analysis. Leach residues and pregnant leach solutions obtained were analyzed chemically as explained previously. Meanwhile, the resultant pregnant leach solutions were also analyzed for residual acid. Oxidation reduction potential (ORP) and density measurements were also performed. During the residual free acid determinations, 0.2 M sodium hydroxide (NaOH) solution was used to neutralize the free acid which remained in the pregnant leach solution. In order to suppress the interfering effect of some ions during titration, 280 g/L di-potassium oxalate monohydrate (K2C2O4H2O) solution was used as a chelating agent during the titration. At the same time the pH meter was calibrated to pH 7.0 by a special buffer solution. The titration procedure was as follows; 20 cc of 280 g/L di-potassium oxalate monohydrate solution was diluted with 5 cc of deionized water and the pH of this mixture was measured with the precalibrated pH meter. Then, 5 cc of pregnant leach solution was added into this mixture and the solution was homogenized by the help of a magnetic stirrer. Finally, this solution was titrated with 0.2 M sodium hydroxide solution to the initial pH level. Then, from the amount of sodium hydroxide consumed, the residual acid in the pregnant leach solution was determined. For the oxidation reduction potential measurements, a Pt-Ag/AgCl electrode (saturated with KCl) was used and the measured values were reported according to the Pt-Ag/AgCl reference electrode. 2.3. Experimental parameters studied Throughout the experiments various process parameters were studied. Initially, the experiments began with the investigation of the effect of leaching temperature on nickel and cobalt extractions. Then the effects of leaching duration, sulfuric acid/ore ratio (w/w), and particle size were examined. In addition to these basic process parameters, the effect of prior heat treatment and the effects of various additives were studied and the list of process parameters investigated is summarized in Table 1. 3. Results and discussion 3.1. Characterization results

High pressure acid leaching experiments were conducted in a Parr-4532 model, 2 l, titanium grade-4 autoclave which was equipped with automatic heating and cooling units, and a magnetically driven stirring system. To test the ore sample, a slurry of 150 g of limonitic nickel laterite ore was prepared with deionized water according to a predetermined solid/liquid ratio of 30 wt.% solids. After the slurry was prepared in the autoclave, technical grade sulfuric acid (9698 wt.%) was added and the lid of the autoclave was closed carefully in order to prevent any leakage during the high pressure leaching operation. At this point, any analytical reagent (AR) of high purity, to test its effect on leaching, was also added before sealing the autoclave, and the system was allowed to heat up to the desired set-point temperature. The start of the reaction, dened as zero time, was dened as when the reactor temperature reached the set-point and the reaction was left to pro-

The bulk and solid densities of the representative Grdes limonitic nickel laterite ore were found to be 1.04 and 3.26 g/cm3, respectively. According to the moisture content measurement, it was calculated that the sample contained 23.47% of physically held water. This suggested that it would be a very energy intensive process just in terms of moisture content if a pyrometallurgical processing route was selected for the treatment of this ore. Chemical analysis of the limonitic nickel laterite sample is given in Table 2. By combining the chemical analysis results together with XRD and DTA/TGA ndings, it was found that the limonitic sample contained high amounts of quartz (SiO2), hematite (Fe2O3), and goethite (FeOOH) minerals as well as the mineral smectite, having the idealized mineral formula of (Na0.3Fe2(Si,Al)4O10(OH)2nH2O). In order to verify the previous analyses, SEM studies on the laterite

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Table 1 List of process parameters studied during HPAL experiments. Experiments Leaching temp. (C) Leaching duration (min) Sulfuric acid/ore ratio (w/w) Particle size (l) Prior heat treatment HCl addition (kg/ton dry ore) Na2SO4 addition (gpl) FeSO4 addition (gpl) Cu+ addition (gpl) Sulfur addition (kg/ton dry ore) Fixed parameters 60 min, 850l, 0.3 acid/ore ratio 255 C, 850l, 0.3 acid/ore ratio 255 C, 60 min, 850l 255 C, 60 min, 0.3 acid/ore ratio 255 C, 60 min, 850l, 0.3 acid/ore 255 C, 60 min, 850l, 0.3 acid/ore 255 C, 60 min, 850l, 0.3 acid/ore 255 C, 60 min, 850l, 0.3 acid/ore 255 C, 60 min, 850l, 0.3 acid/ore 255 C, 60 min, 850l, 0.3 acid/ore Studied parameters 245, 250, 255, 260, 265, 270 0, 60, 90, 180, 360 0.275, 0.300, 0.325, 0.350 38, 425, 850, 1400, 2000 Limonite heat treated at 350 C 33.33, 66.67 12.5, 25.0 14.3, 28.6 1, 2, 3 1, 2, 3 Additive No addition No addition No addition No addition No addition HCl (37 wt.%)(AR) Na2SO4 (AR) FeSO4 (AR) Cu2O (AR) S (AR)

ratio ratio ratio ratio ratio ratio

Table 2 Chemical analysis of limonitic nickel laterite sample. Constituent Content (wt.%) Constituent Content (wt.%) Fe 28.70 SiO2 28.8 Ni 1.28 MgO 2.26 Co 0.083 CaO 1.27 Cr2O3 1.99 K2O 0.12 MnO 0.59 TiO2 0.13 As 0.68 CuO 0.04 Al2O3 5.83 S 0.43

sample indicated that the nickel was mainly present in the crystal lattices of the minerals goethite (FeOOH), hematite (Fe2O3), serpentine ((Mg, Fe)3Si2O5(OH)4) and smectite (Na0.3Fe2(Si, Al)4O10(OH)2nH2O). Cobalt, however, was mainly present in the crystal structure of the mineral asbolane having the idealized formula of (Co, Ni)1y(Mn4+O2)2x(OH)22y+2xnH2O. Similar results were reported by Bykakinci for Grdes limonites in a previous study (Bykakinci and Topkaya, 2009). 3.2. Extraction results The effect of temperature on the degree of nickel and cobalt extractions was initially investigated and then the effects of leaching duration, sulfuric acid/ore ratio and particle size were tested separately in order to obtain the optimum nickel and cobalt extractions with the most cost effective process parameters. The overall results of these experiments are discussed in the following sections. 3.2.1. Effect of temperature According to the extraction behavior of nickel with increasing temperature, it was noticed that there was an increasing trend in the extraction of nickel with the process parameters given in Table 1. However, beyond 265 C this increasing trend seemed to disappear with further increase in temperature. Georgiou and Papangelakis in 1988 reported similar behavior between the temperatures of 230 and 270 C. A study conducted by Chou et al. in 1977 showed that leaching up to 275 C increases nickel yield, but leaching conducted at 300 C leads to a decrease in the degree of nickel extraction. The cause of this behavior was reported in the literature by indicating that in excess of 270 C, the possibility of nickelmagnesium sulfate (Mg, Ni)SO4H2O co-precipitation increases severely due to the lower solubility of magnesium at higher temperatures (Whittington and Muir, 2000). This precipitation is generally accompanied with nickel and cobalt losses to the precipitate. It is also reported that as the temperature of pressure leaching goes beyond 280 C, the possibility of Fe(OH)SO4 (basic iron sulfate) and Al(OH)SO4 (basic aluminum sulfate) formations increase, with accompanied acid losses which are not desirable during the pressure acid leaching process. When the extraction behavior of cobalt is considered, it is seen from Fig. 1 that cobalt is not as sensitive to increasing process temperatures as nickel and its intensity decreases beyond 265 C.

When this result is compared with the reported data in the literature, it is evident that almost 80% of the cobalt is rapidly taken into the leach solution, possibly due to the presence of cobalt in the readily-leached manganese mineral ((Co, Ni)1y(MnO2)2x(OH) 22y+2xn(H2O)), asbolane (Georgiou and Papangelakis, 1998). Georgiou and Papangelakis (2009) showed that treating lateritic ore between the temperatures of 230 and 270 C had essentially no effect upon the rate of cobalt extraction. Cobalt was leached readily in the rst 10 to 20 min of leaching, and its dissolution rate slowed down thereafter. Chou et al. also emphasized the high initial rate of cobalt extraction. Therefore, the extraction behavior of cobalt is generally reported to be less affected by increasing temperature (Chou et al., 1977). Other than nickel and cobalt extractions, it is interesting to note that as a result of increasing leach temperatures, remarkable changes in the extractions of iron, aluminum and, to a limited extent, chromium were observed. This is as a result of temperature rise in the pressure leach process, the precipitation rates of iron and aluminum increasing in parallel with temperature with inverse solubility of hematite and alunite precipitates. This has also been supported by Georgiou and Papangelakis (1998) who report that the increasing leaching temperatures favor increasing nickel and cobalt concentration ratios [(Ni or Co)/(Fe + Al)] as a result of the inverse solubility of hematite and alunite in the pregnant leach solution. The pressure acid leach experiments conducted at different leaching temperatures showed that more nickel and cobalt could be extracted into the pregnant leach liquor in just 1 h of leaching at higher leaching temperatures in the autoclave. However, since higher leaching temperatures mean higher initial investment and operational costs, the optimal process temperature should be selected whether or not the extra nickel and cobalt credit compensates for the former production expenses. Therefore, for the rest of the tests a leaching temperature of 255 C was selected, and higher nickel and cobalt extractions were obtained by optimizing the other process parameters effectively. 3.2.2. Effect of leaching duration The data obtained from leaching duration experiments showed that the nickel and cobalt behaved similarly when the leaching duration was prolonged. It is shown in Fig. 2 that from the starting point, up to 180 min of leaching duration, the nickel and cobalt extractions increased as intended. However, although increasing nickel extraction continued from 180 min up to 360 min of leaching duration, this

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Fig. 1. Effect of temperature upon degree of nickel and cobalt extractions.

Fig. 2. Effect of leaching duration upon degree of nickel and cobalt extractions.

trend resulted in an extraction value of around $95%, which suggested that further increase in leaching duration would be of limited use in increasing the degree of nickel and cobalt extractions. Thus, it was thought that, together with a problem related with the kinetics of the chemical reactions, a persistent leaching behavior limited the process. In other words, these results suggested that there may be very acid resistant refractory minerals present in this limonitic nickel laterite sample which prevented the leaching of nickel and cobalt from the lattice of these minerals. When the mineralogical characterization step is referred to again, the presence of hematite within the limonitic sample appeared to be the possible reason for this extraction behavior. This difculty in the leaching behavior of hematite was also reported by Kui Lui et al. who stated that leaching becomes more difcult among the nickel containing minerals in the following order; Lizardite > goethite > maghemite > magnetite > hematite > chromite % ringwoodite (Liu et al., 2009, 2010). Therefore, this incomplete extraction of nickel stemming from the primary hematite was examined throughout this study to see whether it is possible to overcome this problem. Apart from nickel and cobalt, marked decreases in the extraction of iron, aluminum and chromium were observed after prolonged leaching, due to increased precipitation reactions favored by extended leaching.

The pressure acid leach experiments conducted at different leaching durations showed that more nickel and cobalt could be extracted into the pregnant leach liquor at 255 C by increasing the duration of leaching in the autoclave. However, as in the case of temperature, there was a limit to this increase, possibly due to the difculty in leaching refractory minerals suspected to be mainly hematite. Therefore, prolonged leaching may be helpful in increasing the desired level of nickel and cobalt extractions. However, since prolonged leaching decreases the overall capacity of the plant and thus increases the costs, the optimal leaching duration should be selected whether the extra nickel and cobalt credits compensate for the former production expenses. Therefore, for the remaining tests just 60 min of leaching was selected, and higher nickel and cobalt extractions were obtained by suitable additives and optimizing other process parameters more effectively. 3.2.3. Effect of sulfuric acid/ore ratio While examining the results of the effect of sulfuric acid concentration on nickel and cobalt extractions, the amount of residual acid in the pregnant leach liquor after leaching is also of importance. It has been reported from other research that for high nickel and cobalt extractions sufcient free acid should remain in the pregnant liquor in order to maintain the stability of dissolved species and prevent undesired nickel and cobalt losses (Whittington

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Table 3 Free acidity with respect to sulfuric acid concentration. Acid amount (kg/ton dry ore) Free acidity (gpl) 275 39.2 300 41.2 325 44.5 350 44.9

and Muir, 2000). However, while various researchers have reported the positive effect of residual acidity in the pregnant leach liquor, there is also a limiting value to the amount of this residual acid present in the solution. During the solution purication and metal recovery steps this residual acid should be neutralized somehow, CaCO3 often being the most suitable reactant. Therefore, the amount of residual acid becomes directly related with the consumption of basic reagent and, in turn, it determines the viability of the process economics in terms of the rising cost of consumables. Practical data from various processing plants help to clarify the above. Testwork on Ramu ore at 250 C suggests that 30 g/L of residual acid was optimal for sufcient nickel and cobalt extraction. Similarly, 3040 g/L and 40 g/L of free acid were necessary for Bulong and Murrin Murrin ores respectively (Whittington and Muir, 2000). Therefore, for Grdes limonitic nickel laterite ore 40 g/L residual sulfuric acid was targeted for satisfactory results. The actually measured residual acid values are given in Table 3. Therefore, when the nickel and cobalt extraction results in Fig. 3 and the residual acid measurement values in Table 3 are evaluated together, 300 kg of sulfuric acid per ton of dry limonitic nickel laterite ore seemed to be the most appropriate selection among the other alternatives, since the extra acid addition did not satisfy the required increase in extraction values, in fact increasing the acid and base consumptions pointlessly. In addition to the above, the leach residue samples were analyzed by XRF and the sulfur contents of the leach residue samples were also determined. According to the obtained results, the sample leached with 300 kg of sulfuric acid was found to contain 1.89% sulfur, whereas the sample leached with 350 kg of sulfuric acid contained 2.25% sulfur, which showed that the increased sulfuric acid addition also increased the sulfur losses in the leach residue needlessly. Therefore, this nding also showed that the addition of 300 kg of sulfuric acid would give the best result when the overall considerations were taken into account. 3.2.4. Effect of particle size The results of particle size experiments given in Fig. 4 show that the responses of nickel and cobalt extractions were positive when ner particles were fed into the autoclave. As seen from Fig. 4, the

particle size became more important in terms of nickel extraction when the feed size was decreased below 425 lm, and further reduction in the particle size seemed to give more effective results. Similarly, the extraction of cobalt was increased in such a way that as the particle size was reduced from 2000 lm to 425 lm, there was an almost linear increase in the cobalt extraction. However, this trend became steeper and led to an exponential increase in the extraction of cobalt into the pregnant leach solution when the size was reduced from 425 lm to 38 lm. This was due to the effect of increased specic surface area of refractory minerals, such as hematite and quartz, containing small fractions of nickel and cobalt, which was veried by scanning electron microscopy of the limonitic nickel laterite sample. In addition to changes in nickel and cobalt extractions, Chou et al. also showed that excessive grinding of the ore created extra surface area, which in turn provided additional nucleation sites for iron and aluminum precipitation. Therefore, the impurity concentration of pregnant leach solution decreased as a result of over grinding. Similar trends in the extractions of iron and aluminum were observed during the leaching experiments. Extractions of iron and aluminum tended to decrease as a result of reduction in the feed size which was in agreement with the statement made by Chou et al. in 1977. When the overall results of the particle size experiments are considered, it can be said that grinding was benecial in terms of higher nickel and cobalt extractions and cleaner PLS characteristics for further downstream processing. However, this is limited by technical and economical reasons, as grinding becomes more difcult and energy consuming when the particle size is reduced excessively. The rheology of the pulp fed into the autoclave is also a very important consideration which should be kept in mind during the nal decision making process. Since the rheological properties and ease of stirring in the autoclave are a function of the feed size it becomes very difcult to provide effective stirring when very coarse particle sized feed is fed into the system. Therefore, in the light of these considerations, the limonitic samples ground to 100% 850 lm were used in the remaining experiments. By using the above mentioned process parameters, 87.3% of nickel and 88.8% of cobalt present in the ore were extracted into the pregnant leach solution and the solution contained 4677 ppm Ni, 266 ppm Co, 2620 ppm Al, 1364 ppm Mn, 4754 ppm Mg, 98 ppm As, 123 ppm Cr, and 2296 ppm Fe. 3.2.5. Effect of prior heat treatment Previously the effects of temperature, leaching duration, acid/ ore ratio, and particle size on nickel and cobalt extraction results

Fig. 3. Effect of sulfuric acid concentration upon degree of nickel and cobalt extractions.

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Fig. 4. Effect of particle size upon degree of nickel and cobalt extractions.

have been described and further tests were then performed at 255 C with 0.30 acid to ore weight ratio, with a particle size of 100% 850 lm for 1 h duration. When these optimum parameters were used and the leach residue sample was analyzed by XRD, it was found (Fig. 5) that there were no considerable changes in the quartz peaks after leaching, showing that quartz had remained almost intact during the leaching operation. However, the characteristic peaks of smectite and goethite within the limonitic nickel laterite ore had disappeared, indicating that these minerals were leached out from the original ore sample. After leaching, the intensity of the characteristic hematite peaks increased in the XRD pattern of the leach residue, verifying that iron had tended to precipitate in the form of secondary hematite. Therefore, it is likely that nickel present within the primary hematite mineral may be the main reason for the low extraction results experienced with these limonitic nickel laterite samples. In order to verify this, the

limonitic sample was heated to 350 C in order to transform all the goethite to hematite. The selection of heat treatment temperature was based on the thermal analysis result for the limonitic sample given in Fig. 6. As clearly seen in Fig. 6, at about 270 C goethite present in the limonitic sample has transformed into hematite according to the dehydroxylation reaction of goethite. However, in order to be on the safe side, the heat treatment temperature was chosen as 350 C. The nickel and cobalt extraction results obtained after pressure leaching for the heat treated limonitic ore are given in Fig. 7 together with those of the original ore obtained under the same experimental conditions, for comparison purposes. It is obvious from Fig. 7 that on transforming the goethite to hematite, there was a tremendous decrease in the extraction of nickel and cobalt which means that it is more difcult to leach and obtain nickel from hematite compared with goethite. Moreover, a scanning electron microscopy study on the leach res-

Fig. 5. XRD result comparison of limonite ore and its leach residue.

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Fig. 6. DTA/TGA analysis results of limonitic sample.

the autoclave should be designed to endure the severe corrosive leaching conditions. 3.2.7. Effect of Na2SO4 addition Although some studies report the benecial effects of Na2SO4 addition, the experimental results of Grdes limonitic nickel laterite ore given in Fig. 9 were unsatisfactory due to the observed decrease in the degree of nickel and cobalt extractions. However, the contribution of Na2SO4 in changing the solution impurity concentrations and residue mineralogy could not be ignored, as when the extractions of Fe, Al, Mn, Mg, and Cr in the pregnant leach solution were considered, a remarkable decrease in their amounts was observed. The reason for the decrease of these ions is explained by the increased stability of natroalunite and/or natrojarosite and their precipitation as a result of sodium ions present in the solution (Johnson et al., 2005). In addition to the observed decrease in the concentration of impurity elements, nickel and cobalt may also substitute into the alunite/jarosite structure during precipitation, which may be the reason for the observed low nickel and cobalt extraction values (Whittington and Muir, 2000). Parallel to the formation of natroalunite and/or natrojarosite, the amount of residual acid was measured and it was seen that the free acid in the solution continuously decreased from 41.2 gpl to 37.8 and 33.9, respectively as a result of increases in the Na2SO4 concentration. The decrease in residual acid and the formation of natroalunite and/ or natrojarosite were explained and formulated according to the chemical reactions given below (Johnson et al., 2005):

Fig. 7. Effect of prior heat treatment upon degree of nickel and cobalt extractions.

idue has also shown that the losses of nickel were mainly related to the iron minerals. Therefore, in the following stages, it was attempted to overcome this difculty by making various changes to the leaching environment.

3.2.6. Effect of HCl addition On evaluation of the results of hydrochloric acid addition shown in Fig. 8, the ndings were satisfactory only in terms of increasing the nickel and cobalt extractions, as the extremely corrosive behavior of the acidic mixture resulted in damage to the leaching equipment. As a result of severe acidic attack, some rupture plates on the autoclave have exploded during acid mixture testing which led to the termination of further tests. Thus, the overall conclusion was that HCl together with H2SO4 might be an alternative in order to enhance the extraction behavior of nickel and cobalt from the refractory minerals of the limonitic nickel laterite ore. However,

3Fe2 SO4 3 Na2 SO4 12H2 O ! 2NaFe3 SO4 2 OH6 6H2 SO4 1 3Al2 SO4 3 Na2 SO4 12H2 O ! 2NaAl3 SO4 2 OH6 6H2 SO4 2

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Fig. 8. Effect of HCl addition upon degree of nickel and cobalt extractions.

Fig. 9. Effect of Na2SO4 addition upon degree of nickel and cobalt extractions.

According to these reactions and from the residual acid measurements, the presence of sodium ions in the solution affects the iron and aluminum chemistry and inhibits the regeneration of sulfuric acid to the solution. The changes observed in the reaction chemistry and residue mineralogy also affected the ltration behavior of the leach residue after pressure leaching. As a result of changes in the precipitation reactions, the leach residue showed colloidal behavior during ltration which could be explained by the reduction in free acidity having hydrolyzed the silicic acid to colloidal silica, which in turn complicated the solidliquid separation process (Whittington and Muir, 2000). Therefore, although the addition of Na2SO4 was very effective for solution purication purposes, it seemed that this additive would not solve the problem of low nickel and cobalt extraction results. 3.2.8. Effect of FeSO4 addition Various researchers have reported the positive effect of the presence of reducing species in the pregnant leach solution during pressure acid leaching of lateritic nickel resources. Therefore, in this part of the study, the effect of divalent iron addition to the leach solution was investigated in order to enhance the nickel and cobalt extraction values. As stated in the literature, the addition of divalent iron led to a drastic fall in the reduction potential of the leach solution. To be more specic, the reduction potential of

the pregnant leach solution decreased from 489 mV to 366 and 344 mV, respectively after the FeSO4 additions, and this reducing solution led to the desired increase in the nickel and cobalt extraction values, as shown in Fig. 10. This behavior was explained by Tindall and Muir (1997) as the presence of divalent iron species facilitates bond breakage and aids iron oxide dissolution via electron transfer in the leach solution, thus increasing the extraction of valuable metals from the goethite and hematite matrix. Also related to the FeSO4 addition is that the amount of iron present in the leach solution increased due to iron sulfate addition as expected. Before ferrous ion addition, most of the iron in the PLS was in the form of ferric ion. However after this addition the amount of ferrous ion was naturally increased, which is a disadvantage for downstream processes, as iron present in the ferrous state should be oxidized to the ferric state during downstream processes, making the process more complicated. So apart from the negative effect of ferrous ions during the downstream solution purication processes, this addition was effective in enhancing the extraction behaviors of nickel and cobalt on changing the solution characteristics to a more reducing character. 3.2.9. Effect of Cu+ addition After obtaining somewhat encouraging results from the FeSO4 addition experiments, further tests to evaluate the positive effects of reducing solution characteristics were attempted with the

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Fig. 10. Effect of FeSO4 addition upon degree of nickel and cobalt extractions.

addition of cuprous ions (Cu+) into the leach solution. The catalytic mechanism of cuprous ions is correlated with the ease of electron transfer between Cu+ and iron species. According to the proposed mechanism in the literature, the dissolution of iron species in the presence of cuprous ions is catalyzed by the following electrochemical reaction, while nickel present within the crystal lattice of iron minerals is predicted to be liberated into the solution (Byerley et al., 1979; Parker and Espenson, 1969);

ion addition. According to Fig. 11, only a slight increase in the extraction of cobalt was observed when compared to nickel. This was due to higher ORP values obtained in the case of Cu(I) additions as a result of the signicant variation of FeSO4 to Cu(I) concentrations in the liquor. 3.2.10. Effect of S addition Experimental evidence up to this stage has shown that there is a close relationship between the electrochemical nature of the leaching solution and the observed nickel and cobalt extractions. To conrm this, the same constant test parameters were used as in the case of ferrous and cuprous ions additions, and the addition of sulfur to change the reduction potential of the leach solution was planned in order to facilitate electron transfer in the solution. For the no-sulfur added experiment the reduction potential was 489 mV. However, on addition of sulfur the reduction potentials were measured as 373, 349, and 334 mV, respectively with increasing sulfur content. Thus sulfur seemed to be very effective in controlling the reduction potential of the leach solution. According to the results given in Fig. 12, almost the same extractions of nickel and cobalt were observed as in the case of cuprous ion addition. Slight increases in the extractions of nickel and cobalt were believed to be the result of more reducing solution characteristics.

Fe3 Cu ! Fe2 Cu2

According to the results shown in Fig. 11, the positive effect of cuprous ions in extracting the nickel present in the hematite crystal lattice was similar to that of previous studies performed by other researchers. In the case of cobalt, previous work has shown that the extraction of cobalt can be enhanced when the potential of the solution is adjusted to a more reducing character (Tindall and Muir, 1997). This was veried by the addition of reducing ferrous ions into the leach solution. On addition of cuprous ions in increasing amounts, the reduction potential of the solution was lowered from 489 mV to 449, 440, and 410 mV, respectively. However, the expected enhancement in extraction behavior of cobalt was not as good as that obtained by ferrous

Fig. 11. Effect of Cu+ addition upon degree of nickel and cobalt extractions.

S. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 11881197

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Fig. 12. Effect of S addition upon degree of nickel and cobalt extractions.

4. Conclusions In this experimental study the basic HPAL process parameters, such as leaching temperature, leaching duration, sulfuric acid to ore weight ratio and particle size of a limonitic nickel laterite ore were studied. The observed enhancement in the degree of nickel and cobalt extractions with increase in leaching temperature and duration, together with decreased particle size, have shown that, together with a problem related to the kinetics of the chemical reactions, a persistent leaching behavior also limited the process. On optimizing the basic HPAL process parameters leaching at 255 C with 0.30 sulfuric acid to ore weight ratio with a particle size of 100% 850l for 1 h, it was found that 87.3% of nickel and 88.8% of cobalt present in the ore could be extracted into the pregnant leach solution. However, these results were found to be below the desired values. Therefore, the possible reasons for this behavior were investigated and the presence of difcult to leach hematite mineral was found to be the most probable one. Heat treatment of the limonitic nickel laterite ore prior to leaching has shown that goethite present in the ore had fully transformed to hematite and after this transformation a tremendous decrease in the nickel and cobalt extractions was observed. Therefore, in order to dissolve the nickel and cobalt present in the difcult to leach hematite mineral present in the limonitic nickel laterite ore, additions of HCl, ferrous ions, cuprous ions and sulfur were tried, respectively. The data obtained for the overall extraction with the various additives showed that the improvement of nickel and cobalt extractions was $3%. Acknowledgements The authors would like to express special thanks to META NikelKobalt A.S. both for supplying the limonitic nickel laterite ore sam ple of Grdes and for doing the chemical analyses by XRF and AAS. Also, METU Center Laboratory for DTA-TGA analyses and METU Metallurgical and Materials as well as Chemical Engineering Departments for performing XRD and AAS analyses are gratefully acknowledged.

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