Hydrometallurgy 99 (2009) 84–88

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Effect of pre-roasting on leaching of laterite
Jinhui Li a,b, Xinhai Li a,⁎, Qiyang Hu a, Zhixing Wang a, Youyuan Zhou a, Junchao Zheng a,
Wanrong Liu a, Lingjun Li a

School of Metallurgy Science and Engineering, Central South University, Changsha, Hunan Province, 410083, PR China
School of Materials and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou, Jiangxi Province, 341000, PR China

a r t i c l e

i n f o

Article history:
Received 23 November 2008
Received in revised form 8 June 2009
Accepted 4 July 2009
Available online 5 August 2009
Gamierite laterite
Hydrochloride acid
Phase transformation

a b s t r a c t
The effect of pre-roasting on leaching of the gamierite laterite ore, obtained from Yunnan province, China,
was investigated in this study. The phase transformation of laterite minerals roasted at different
temperatures was investigated with X-ray powder diffraction (XRD). The roasting experiment results show
that there are two phase transformation processes of dehydroxylation of goethite and lizardite at roasting
temperatures of 277 °C and 610 °C, respectively, which accord with the result of DTA–TG analysis. Preroasting of the laterite not only alters its mineralogical composition but also increases its porosity and surface
area, thus making it more amenable to leaching. Compared to the leaching result of raw ore and ores roasted
at different temperatures, it indicates that increasing roasting temperature up to 300 °C appears to provide
the optimum nickel recovery and further heating appears to be detrimental to the nickel recovery.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Nickel ranks 24th in abundance while elements such as iron,
silicon, oxygen and magnesium account for over 90% of the earth's
composition. Nickel occurs within both laterite and sulfide ores and it
is also associated with deep-sea nodules (Moskalyk and Alfantazi,
2002). Laterite ores consist of the majority (80%) of the world's nickel
reserves. Although sulfides are still the primary source of nickel and
cobalt, increasing underground costs and decreasing the grades of the
sulfide ores attract more attention towards the exploitation of laterite
ores (Dalvi et al., 2004; Pickles, 2004). However, only 42% of the
world's nickel production comes from nickel laterites (Gleeson et al.,
2003; Sudol, 2005). One of the major economic factors, which limit
the development of the laterite ores, is that the energy costs for
processing these ores are 2–3 times higher than that for the sulfide
ores (Thomas, 1995). Therefore, in the long term it will be necessary to
develop new processing techniques, which are both technically and
economically viable.
Roasting with addition of reductant such as sulfur, carbon, and
other reducing gas is a popular method in dealing with laterite (Valix
and Cheung, 2002; O'Connor et al., 2006) since the standard reductive
roast/ammoniacal leach process initially defined by Caron (1924) has
proven satisfactory in treating most low-grade nickel laterite oxide

⁎ Corresponding author. Present address: School of Metallurgy Science and
Engineering, Central South University, Changsha, Hunan Province, 410083, PR China.
Tel.: +86 731 8836633.
E-mail address: bigworld_li@163.com (X. Li).
0304-386X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.

ores, and pre-roasting has a significant influence on the following
reduction process (Valix and Cheung, 2002; Swamy et al., 2003;
O'Connor et al., 2006). Pre-roasting can change the mineral structure
(Ruan et al., 2002), and Valix and Cheung (2002) even proved that
pre-roasting can lead to the dehydroxylation of the serpentine or
magnesium hydrosilicate phase and form an amorphous magnesium
silicate phase. And dehydroxylation of goethite due to heating causes a
topotactic transformation to hematite which occurs via minor
modification in the goethite structure (Landers and Gilkes, 2007).
Moreover, due to the removal of free and combined moisture and
collapse of partial phase structure, roasting can alter its mineralogical
composition and increase the surface and porosity of the raw ore, thus
making it more amenable to leaching (Olanipekun, 2000). Although
the importance of mineral dehydroxylation and phase transformation
in metal leachability of reduced laterite has been suggested by the
studies of De Graff (1979, 1980), Kukura et al. (1979), Valix and
Cheung (2002) and O'Connor et al. (2006) in the reduction of silicate
laterite minerals, the mechanism of pre-roasting in different metals
leachability and selectivity of gamierite laterite ores with hydrochloride acid as leachant is seldom studied in literatures. In this
present study, an attempt has been made to identify the mechanism of
pre-roasting on leaching of laterite in hydrochloride acid solution and
efforts have been likewise made to extract nickel selectively over iron
by a roast–leach process. Although leaching with various acids was
studied by McDonald and Whittington (2008a,b), and due to mainly
economical reasons sulfuric acid was preferred. In this leaching
process, a particular advantage is that hydrochloric acid as a leachant
allows comparatively easier recovery of the useful free acid from its
waste solution than does sulfuric acid. Moreover, separation of metal

3. 3. and the highly corrosive nature of the hydrochloric acid was overcome by using aceramic-lined continuous digester (McDonald and Whittington.. Rint-2000. Results and discussion 3. CM. 1997). goethite transforms to hematite as shown in Eq. Volumetric analysis (K2Cr2O7 titration) was employed for Fe.346 57. The cooled roasted ore was then transferred into a leaching pod containing 4 mol/l hydrochloride acid solution which had been heated to the desired temperature and the timing was initiated. The effect of roasting on mineral transformation of laterite ores under atmospheric pressure at different temperatures is shown in Fig.341% and 7.i = iP −1 i=1 ! vi CM. 1. With considering chemical composition of raw ore shown in Table 1.01 0.4 0.2. Table 1 Chemical composition of raw ore. The air was metered into the reactor using rotameters before the temperature began to increase. Constituent NiO CoO MnO Fe2O3 CuO MgO Al2O3 SiO2 Content (wt. 2.1°. The specific surface area of the ores was determined through BET nitrogen–helium absorption method. It appears that the lizardite dehydroxylation is .5 °C). Co and etc. 3(a) and (b). The main minerals. respectively. The leaching experiments were performed in a 250-ml round-bottom flask with 3 holes.042 0.007 26. In this study. After roasting was completed. 1982) and 337 °C (Swamy et al. 1. The temperature of the ores during roasting was monitored using a sheathed thermocouple inserted into the bed. 86-0404). dehydroxylation of goethite and lizardite. Li et al.60 0.06°. a reflux condenser was mounted on top of the cell. A computerized X-ray diffraction equipment (XRD. 2. 18. The reaction temperature was maintained constant with a thermostatically controlled water bath. At 277 °C. 2002). The lower decomposition temperature of laterite in this study is indicative of poorly crystalline goethite structure. The weight loss corresponding to these two processes are 4. Mineralogical analysis The DTA–TG curve of the raw ore is shown in Fig. where V is the initial volume (ml) of the solution. there are some reactions and structure changes that occurred.%) 0. M represents metal.. The solid residue was washed with distilled water and dried in an oven overnight at 105 °C. This is evident by the formation of broad peaks and eventual loss of X-ray diffraction signals for the lizardite minerals at 2θ angle of 12. The analysis of the final solid residue provided a confirmation of the overall metal recovery after leaching.64°. DTA–TG analysis shows two endothermic peaks at about 277 °C and 607 °C due to the release of adsorbed water. the ores were ground to 100% passing 100 mesh. / Hydrometallurgy 99 (2009) 84–88 85 chlorides through solvent extraction (SX) is much easier than from sulfate medium (Olanipekun. νi is the volume (ml) of sample i withdrawn each time. such as TG (thermo gravimetric). The stirring speed (300 rpm) which gave sufficient mixing was kept constant in all the experiments. equipped with a digitally controlled thermometer (within ± 0. V− XM. XRD (X-ray diffraction). which are evident from the X-ray diffraction pattern shown in Fig. Results of this research may assist in the development of more efficient procedures for processing oxide-type lateritic nickel ores. The dried residue was digested in aqua regia solution (1:3 HNO3/HCl) for 2 h (O'Connor et al. 2. where the laterite mainly consisted of three layers in order of increasing depth: a hematite cap. the result was calculated in formula (1). Materials preparation and characterization The ores tested in this study originated from Yunnan province in China. 2. referred to the JCPDF file No. The digest solutions were also analysed for dissolved metals using atomic absorption spectroscopy and volumetric analysis. referred to the JCPDF file No.43 Fig. Roasting and leaching Roasting was conducted in a fixed tube furnace. analysis of Ni. (2) (Valix and Cheung. a limonitic laterite deposit and finally garnieritic ore. m is the initial mass of laterite in g (on dried basis) added into the reactor and cM is the concentration of M in laterite (wt. AAS (Atomic Absorption Spectrometry) and SEM (scanning electron microscope).618%. In reference to Fig.i mðcM = 100Þ : ð1Þ X is the metal dissolution.i is the concentration of M (Ni. lizardite (Mg3Si2(OH)4O5) discomposes and forms an amorphous magnesium silicate phase.174 15. For minimizing aqueous loss when the system was heated. The typical chemical analysis of these ores is shown in Table 1. After drying in vacuum overnight at 105 °C.% dried solids). 24. respectively (Tartaj et al. some determination methods are carried out to study the mechanism. 2000). Analysis For all the experiments. are lizardite (Mg3Si2(OH)4O5. Mn and Co employing standard procedures was carried out by atomic absorption techniques type of Ruili-wfx120.38° and 60. referred to the JCPDF file No.3. 2008b). 3. the ores tested are mainly garnieritic laterite ore. 89-0597) and quartz (SiO2. And the effect of leaching time on nickel extraction was also investigated. hematite (Fe2O3.1. 83-0539).J. Powder XRD pattern of raw laterite. 2000. Gibson and Rice. Rigaku) using CuKa radiation was used to identify components of raw ore and roasted ores.1.) in sample i (mg l− 1). which can be observed from the difference between Fig.i + iP −1 i=1 vi CM. At roasting temperature of 607 °C.. This decomposition temperature is low compared to the decomposition temperature of 385 °C (Schwertmann et al. goethite (FeO(OH). 81-0462).. referred to the JCPDF file No. Experimental 2. 2003) often associated with highly crystalline goethite. the Ar gas was metered into the reactor continuously until the ores cooled down. 2006).

f: roasted at 700 °C. This is why there is no nickel loss by leaching ores roasted at different temperatures (300 °C. so the specific surface area of ores roasted at 400 °C and 500 °C decreases to 19. Whittington and Muir. 400 °C and 500 °C). And more fine pores and scraps can be found on the surface from Fig.45 m2/g. 1981). 2 and 3.. in which metal cations are leached without appreciable release of silica (Kosuge et al. (2003) and Whittington and Johnson (2005) examined nickel losses in the leach residue by pressure acid leaching of arid-region laterite ore and found that cations like Ni2+ were adsorbed on amorphous silica. 3. It suggests that further heating appears to be detrimental to the nickel recovery. the specific surface area attains the maximum 26. Brand et al. the nickel recovery decreases slightly. Due to the inclusion of nickel in the recrystallised iron oxide (O'Connor et al. On the surface are highly reactive groups. 4(a) and (b) that there are more fine pores and scraps on the surface of ore roasted at 300 °C than that of raw ore surface. above 610 °C.618% due to the loss of water which can be explained in Eq.61 m2/g and 13. 2008). The leaching results were shown in Table 2. It can be seen that the nickel dissolution can attain the maximum value with the ore roasted at 300 °C. the specific surface area of ore roasted at 300 °C increases to 21. Due to the phase transformation.. which is shown in Table 3. When roasting temperature is 610 °C. . With leaching of the ore roasted at 610 °C. 2007. 2 and 3(d) and (e). At the same time. which is shown in Figs. d: roasted at 500 °C. leaching conditions.. Therefore. In contrast. TG–DTA curves of laterite. In order to investigate the effect of leaching time on nickel extraction. 2000. 2002). On the one hand. 1998). 4(a) and (b). the specific surface area decreases to 18. 4(c) compared to that of Fig. On the other hand. the weight loss is 7. Chander and Sharma (1981). 5 that the nickel extraction of leaching ore roasted at 610 °C can reach about 83% after leaching for 20 min and then somewhat decrease which suggests that the nickel loss is due to the nickel absorption by amorphous silica in the solution. leaching time = 1 h. This large surface area and surface energy means that colloidal silicic acid is an excellent adsorbent which takes up ions or molecules of gas or liquid (Reig et al. Lin and Clemency. studies of the characteristics of the limonite minerals with temperature. Similarly. temperature = 50 °C. completed at temperature about 607. the raw ore was also tested in the same Fig. the amorphous magnesium silicate phase appears to have recrystallised as forsterite (Mg2SiO4) and enstatite (MgSiO3) shown in Fig. it is postulated by O'Connor et al.03 m2/g of raw ore shown in Table 3. And nickel bound within goethite grains usually requires complete dissolution of the grain to achieve high nickel extraction (Senanayake and Das.. (3). suggested that increasing the temperature could reduce the porosity of the ore. 1981). silicon. oxygen and hydrogen (Si–O–H). the main mineral lizardite (Mg3Si2(OH)4O5) begins to discompose. c: roasted at 400 °C. As roasting temperature increases to 700 °C and even 800 °C. 2004). it may be due to nickel loss partly in the leach solution (Wei et al. 2006). But the unexpected result is that nickel recovery decreases to 77%. Whittington et al. g: roasted at 800 °C). it may be due to some fine particles reunite together (Chander and Sharma. 2FeO·OH→Fe2 O3 þ H2 O↑ ð2Þ Mg3 Si2 ðOHÞ4 O5 →Mg2 SiO4 þ MgSiO3 þ 2H2 O↑ ð3Þ 3.2. at higher temperature.04 m2/g compared to 16. 2008). leading to mineral structure destroyed.. 3(e) and (f). On heating. plenty of silicic acid particles characterized by a very large surface area are dispersed in the leaching solution and Wei et al.23 m2/g.21 and 19. at fixed leaching conditions: Solid/liquid ratio = 1:6. Powder XRD pattern of minerals induced by heat at atmospheric pressure (a: raw ore. 2. It can be seen through Fig. / Hydrometallurgy 99 (2009) 84–88 Fig.13 m2/g slightly. (2006) that the lower nickel recovery is due to the inclusion of nickel in the recrystallised iron oxide and the leaching conditions are not sufficient. Li et al. Literature on the acid extraction of saprolitic ores under AL conditions implies that serpentine minerals dissolve by partial decomposition of the silicate structure (known as incongruent dissolution). DTA–TG displays an additional exothermic peak at 807 °C associated with forsterite (Mg2SiO4) recrystallisation (Wei et al. the nickel recovery decreases to 31.5 °C which can be discovered from Figs. this results in the release of nickel or more nickel is exposed to the reaction interface which is more susceptible to attack. b: roasted at 300 °C. And it also can be found through Fig. which had a strongly negative surface charge.. It indicates that Ni is uniformly incorporated in the goethite structure which comprises the dominant Ni host mineralogy (Senanayake.86 J. respectively. e: roasted at 610 °C.25% and 31. even in the presence of Mg2+ cations. 1995. a series of leaching experiments were performed with the leaching time varied from 5 to 60 min under the same experimental conditions too. (2008) ever confirmed the formation of amorphous silica from XRD pattern and FTIR spectrum of the leach residues. goethite transforms into hematite roasted at about 277 °C leading that the structure of original mineral is changed or destroyed.1%. Leaching results The cooled roasted ores were then transferred into a leaching pod containing 4 mol/l hydrochloride acid solution.

04 19. c: roasted at 610 °C. Increasing the temperature up to 300 °C for gamierite laterites which originated from China appears to provide the optimum nickel recovery. The order of leaching rate can be well in accord with the order of specific surface area. Li et al. Conclusions The results suggest that roasting temperature can have a significant effect on the nickel metal recovery because it mainly exists in goethite phase.1 67.3 40.2 40 40.97 2. which renders it inert and hinders further release of nickel trapped in this phase (Valix and Cheung. 5.1 39. it will probably lead to the incorporation of iron into the magnesium silicate phase (Mg. 2006)..5 10 24.45 78 65 32. SEM image of laterite (a: raw ore.76 1. 3.1 40 99. The leaching of cobalt and manganese is not influenced markedly by roasting temperature shown in Table 2.1 2.9 98.3 75.4 61.43 1.6 61. The experiment results show that heating may lead to the incorporation of nickel into the magnesium silicate phase (Mg.24 98.8 39. 3(f) and (g).7 71. b: roasted at 300 °C. 4.56 Table 3 Specific surface area of raw ore and ores roasted at different temperatures.1 98.Fe)3SiO2 followed by recrystallisation into the forsterite phase which hinders further release of iron trapped in this phase.4 98.3 40.82 0. 4.Ni)3SiO2 followed by recrystallisation into the forsterite phase shown in Fig. As for Fe.23 Kukura et al.1 92.61 13. Sample Raw ore 300 °C 400 °C 500 °C 610 °C 700 °C 800 °C % Ni % Co % Mn % Fe Solution Residue Solution Residue Solution Residue Solution Residue 33 93.46 4. it indicates highly crystalline hematite transformed from goethite shown at 2θ angle of 33° with heat increasing in Fig.9 67. its extraction shows a decreasing trend with the increase of roasting temperature.J.5 30 26 29 20 22 34. . Especially when roasting temperature is over 610 °C while lizardite begins to dehydroxylate. Because pre-roasting opens the main gangue mineral structure and goethite.5 95 0. This implies that the structure which comprises the dominant Co and Mn host mineralogy in the ore is not changed or destroyed significantly by roasting.1 7.2 60. 2002.45 18. and further heating is detrimental to the Fig.13 26.23 59.3 98. Raw ore 300 °C 400 °C 500 °C 610 °C 700 °C 800 °C Specific surface area (m2/g) 16. / Hydrometallurgy 99 (2009) 84–88 87 Table 2 Effect of roasting temperature on leaching results after 60 min.8 70.35 71. (1979) and Hayashi (1971) inferred that nickel became unstable after dehydroxylation and it was at this stage that the fate of nickel was decided.7 90 77 31. the nickel leaching rate of ore roasted at 610 °C is the maximum.25 31.54 61.6 80. which is similar as nickel dissolution behavior. As is shown in Fig.21 19. O'Connor et al.92 59.03 21.08 68. d: roasted at 800 °C).6 60.8 7. thus allows a rapid interaction between the leachant and the nickel species during leaching.

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