Atmospheric Acid Leaching of Nickel Laterites Review Part I. Sulphuric Acid Technologies
Atmospheric Acid Leaching of Nickel Laterites Review Part I. Sulphuric Acid Technologies
Atmospheric Acid Leaching of Nickel Laterites Review Part I. Sulphuric Acid Technologies
com
Hydrometallurgy 91 (2008) 35 – 55
www.elsevier.com/locate/hydromet
Received 2 April 2007; received in revised form 22 October 2007; accepted 20 November 2007
Available online 28 November 2007
Abstract
This review examines the atmospheric leaching (AL) of nickel laterite ores with sulphuric acid, specifically the limonite,
smectite (clay) and saprolite fractions. The kinetics and mechanism of leaching of the key minerals are reviewed together with
methods for enhancing nickel recovery. Existing and developing AL processes for extracting nickel and cobalt from these ores are
then considered with comparison to high pressure acid leaching (HPAL) technology. This review also provides an overview of the
emerging hybrid HPAL/AL and heap leaching technologies.
Crown Copyright © 2008 Published by Elsevier B.V. All rights reserved.
Keywords: Atmospheric leaching; High pressure acid leaching; Sulphuric acid; Nickel laterite; Nickel processing
generates acid and reduces the overall acid consumption strengths and weaknesses as summarised in Table 1.
of the HPAL process but leaves about 50–60 g/L free acid Reid and Barnett (2002) concluded that for AL to be
in the leach solution. The leach slurry is ‘flashed’ from the competitive with HPAL, it would have to “give good
autoclave, the solids are separated from the liquor by recoveries, allow acceptable acid consumption and pro-
counter current decantation (CCD), the liquor neutralised duce low residual iron in solution”. Griffin et al. (2002)
to remove iron(III), aluminium and chromium(III) and the considered the choice between AL and HPAL to be an
soluble nickel and cobalt are subsequently processed. economic one relating to acid supply cost, the miner-
Atmospheric leaching (AL) at lower temperature and alogy of the ore body and trade offs in recovery versus
in open vessels avoids the need for expensive HPAL lower cost plants. Neudorf (2007) concluded that AL in
autoclaves. However, two key issues are the kinetics of itself may not represent a quantum process development
nickel extraction and the ease with which the liquor can shift and other factors, particularly those related to in-
be processed subsequently. Specifically, the leach liquor frastructure, may require significant improvement. It is
from AL is likely to contain significant concentrations clear from Table 1 that a range of considerations must be
of soluble iron and aluminium and methods must be examined when determining if AL is a viable processing
found to selectively reject these metals from solution or option.
selectively extract nickel and cobalt (Willis, 2007). This review first considers the mineralogy and re-
The case for AL versus HPAL has been debated for activity of nickel laterites including selective leaching of
many years and gives rise to a substantial list of relative various ore types (viz. limonite, smectite, saprolite). It
Table 1
Advantages and disadvantages of atmospheric leaching (stirred tank or heap) as compared to pressure acid leaching
Expected advantages Refs. Expected disadvantages Refs.
Lower CAPEX b, d, e, g, h Higher acid consumption (to obtain a, b, c, d, e, g, h
acceptable nickel recoveries)
Conventional equipment technology c, e, f, h Residue more voluminous (from tank leaching) h
Cheaper (less exotic) materials of construction b, h More magnesium in the waste liquor compared g, h
to limonite HPAL
Lower maintenance costs c, d, e, h May consume more limestone h
Higher plant availability c, h No significant improvement in OPEX (depending upon h
how second generation HPAL plants perform)
Faster ramp-up h Cannot be applied to all ore bodies (mineralogy a, e, f, h
dependent); less effective for treating limonites
Easier start-ups and shut-downs h Not yet commercially proven h
Not prone to “catastrophic” shut-downs h Slower extraction kinetics and hence longer residence times c, d, h
Less specialized workforce for construction, h Produces highly contaminated liquor with significantly b, d, e
operations and maintenance lower nickel to iron ratio; downstream processing
more challenging (e.g. solid–liquid separation)
Many suppliers of major, “common” equipment h Lower nickel and cobalt extractions (esp. from c, d, f
neutralising ores)
Better acid utilisation h Presence of more jarosite in tailings potentially an c, f, g
environmental problem
Lower energy consumption, leaching autogenous b, h Longer residence times c, d, f, g
Simpler energy system h CAPEX still relatively high e
Simpler process control h Requires correct blending of limonite and saprolite e
Easier recycle of process water h Heap permeability critical e
Heap leaching far less complex than HPAL or AL e, h Sulphate losses due to jarosite formation f, g
(e.g. no CCD, no tailings disposal)
May lower cut-off grades h
May be better suited to remote, undeveloped locations h
Process both limonite and saprolite e, f, h
Lesser scale and corrosion problems a, b
Economic if cheap sulphuric acid available a
Use of sea water to provide sodium for iron rejection c, e
Smaller operations allow for substantially lower i
investment with heap leaching
a. Canterford (1979); b. Chander (1982); c. Reid and Barnett (2002); d. Griffin et al. (2002); e. Wedderburn (2005); f. Neudorf and Huggins (2006);
g. Smit and Steyl (2006); h. Neudorf (2007); i. Santos de Pontes Pereira and De Araújo Gobbo (2007).
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 37
then examines developing technologies that focus upon A number of key studies have considered the asso-
the following: ciation of nickel with the various minerals in lateritic
ores although various leaching studies described later
• Methods for improving the AL of nickel laterites provide evidence for the deportment of nickel.
including roasting pre-treatment (other than applic- It was suggested by Swamy et al. (2003) that nickel is
able to the Caron Process and ammoniacal leaching) generally present in goethite in three modes, (i) asso-
• Hybrid HPAL/AL processes that neutralise the free ciated with amorphous or poorly crystalline goethite,
acid in HPAL slurries with reactive ores under AL (ii) weakly adsorbed to the crystalline goethite surface
conditions and (iii) as a substituent in the goethite structure.
• Heap leaching processes. Sequential leaching experiments were used to quantify
these modes in some Indian laterite samples though in
In general, nickel and cobalt bound within goethite, all cases the quantity of chemisorbed nickel was
clay and saprolite ores are processed hydrometallurgi- indicated to be minimal. Trolard et al. (1995) also
cally whilst silicate rich garnierite ores are amenable to found that nickel is not adsorbed onto mineral surfaces.
pyrometallurgical processes to produce high carbon It has been thought for some time that there are no
ferro-nickel (criteria: N2.2% Ni, Fe/Ni ratio of 5–6), low discrete nickel oxides in nickeliferous laterites (Chandra
carbon ferro-nickel (criteria: N1.5% Ni, Fe/Ni ratio of et al., 1983). Similarly, the EXAFS data of Singh et al.
6–12, high SiO2) or matte (criteria: Fe/Ni ratio N6, (2002) provided no evidence for a separate Ni(OH)2
SiO2/MgO ratio 1.8–2.2). It is beyond the scope of this phase but rather that nickel is substituted isomorphously
review to consider the acid leaching of nickel bearing for iron in the goethite structure; the goethite samples
oxide minerals in ocean nodules. were synthesised via two methods thought to imitate
Emerging AL technologies that employ hydrochloric natural processes. Like nickel substitution in hematite
acid and fungal or microbial metabolites (viz. organic (Singh et al., 2000), it was suggested that the charge
acids) are examined in Part II of this review (McDonald balance is maintained by substitution of OH− for O2−.
and Whittington, in press). The maximum level of substitution for divalent nickel
and cobalt in goethite has been reported by Giovanoli
2. Nickel laterite processing and Cornell (1992) to be about 6–7% while for trivalent
ions it can be somewhat higher.
2.1. Mineralogy of the important nickel laterite mineral Nickel laterite deposits even from the same region
phases can be quite variable in nature. The mineralogy of the
smectite zone in Murrin Murrin nickel laterites in
The laterite ore types and chemical formulae of im- Western Australia displays highly variable composition
portant minerals relating to the processing of nickel though the dominant smectite group mineral is non-
laterite ores are presented in Table 2. A summary of the tronite, which is the Fe3+-rich variety. In addition, and
mineralogy of nickel laterite deposits is also given by less commonly, Mg–Fe-rich and Fe-rich montmorillo-
Gleeson et al. (2003). nite, and the Mg-rich variety saponite, have been
Table 2
Ideal formulae for minerals of interest to the nickel refining industry (descriptions from Fleischer, 1983)
Mineral name or type Formula
Alunite/Jarosite (X, Y = Na, NH4, H3O, K) (X,Y)(Al, Fe)3(SO4)2(OH)6
Chlorite (chlorite group mineral; 2:1 clay) Na0.5(Al,Mg)6(Si,Al)8O18(OH)12·5H2O
Garnierite (general term for hydrous nickel silicates) (e.g. falcondoite, (Ni,Mg)4Si6O15(OH)2·6H2O)
Goethite α-FeOOH
Hematite α-Fe2O3
Maghemite γ-Fe2O3
Magnesite MgCO3
Nontronite (smectite group mineral; 2:1 clay) (Na)0.3(Fe3+)2(Si,Al)4O10(OH)2·nH2O
Saponite (smectite group mineral; 2:1 clay) (Ca/2,Na)0.3(Mg,Fe2+)3(Si,Al)4O10(OH)2·4H2O
Saprolite (common name for serpentine group clay minerals)
Serpentine group minerals (1:1 clay) — include antigorite, lizardite, chrysotile Mg3Si2O5(OH)4
Talc (talc group mineral; 2:1 clay) Mg3Si4O10(OH)2
38 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
identified (Camuti and Riel 1996). A suite of other phases. Thus manganese oxide impurities will often be
minerals that includes the nickel hosts chlorite and present in limonites. The affinity of cobalt for these
magnesite, and poorly crystalline silica that contains a impurities has been noted by Manceau et al. (2000) for a
trace of nickel may also be found. Nickel content in the West African laterite fraction and by de Oliveira et al.
nontronite may be up to 4% whereas for the other (2001) for Cuban laterites. In the former study, although
smectite minerals, it is normally no more than 1.5%. it was indicated that Co-sorbed birnessite is probable,
Recent studies (Gaudin et al., 2004a, 2004b, 2005) neither lithiophorite nor asbolane could not be excluded
indicated that the crystal chemistry of the Fe-rich as cobalt-bearing minerals. Both of the latter minerals,
smectites was more complex than previously thought that also host nickel, have been found in the oxidized
and exhibits intermediate chemistries between four di- horizons of New Caledonian nickel laterites (Manceau
octahedral end-members (beidellite, nontronite, mon- et al., 1987). Trolard et al. (1995) on the other hand
tmorillonite and ferric-montmorillonite) and tri-octahe- indicated that only small amounts of nickel, b5% of
dral (Mg + Ni)-saponite. Furthermore, it was shown that the total, were associated with manganese oxides in
nickel does not form discrete phases but substitutes for Burundi nickel laterite samples.
octahedrally coordinated cations in the smectite structure.
The Murrin Murrin saprolite zone contains the ser- 3. Kinetics and mechanism of acid leaching of
pentine group minerals lizardite and chrysotile together laterite minerals
with chlorite clay minerals which have variable nickel
content. Maghemite and varying amounts of smectite There is a significant body of literature that examines
group minerals and silica spheres that can contain traces the kinetics and mechanisms of leaching of minerals
of nickel are also present (Camuti and Riel 1996). The commonly found in nickel laterite deposits using both
nature of smectites in the saprolite zone was subse- sulphuric acid and hydrochloric acid. In most cases, the
quently studied in greater detail (Gaudin et al., 2005). activity of the proton governs the reacitivity rather than
Nickel enrichment of the Cawse deposit laterites is the specific acid therefore both acids are discussed
primarily associated with high-iron-containing zones below and provides fundamental knowledge relevant to
and in particular, iron oxy-hydroxides. However, there both the sulphate and chloride based technologies.
is also a shear zone that hosts nickel-enriched chlorite
and talc-phlogoptite minerals (Brand et al., 1996) and a 3.1. Goethite
lower saprolite zone that hosts lower nickel concentra-
tions and which is dominated by antigorite (Hellsten and It has been reported that the various crystallographic
Stewart 2000). faces of goethite exhibit different rates of dissolution in
The nickel host minerals at the Bulong deposit con- acid (Cornell et al., 1974). This was suggested to relate to
sist of goethite, asbolane-like minerals and smectites, the concentration of singly coordinated hydroxyl groups
which occur in both the smectite (nontronite) and sapro- (i.e. FeOH) which would be expected to be easier to
lite horizons. It would appear that the serpentine min- remove by acid than the doubly or triply coordinated
erals are mostly devoid of nickel (Burger 1996). hydroxyl groups. However, depending upon the shape of
The overall nature of cobalt incorporation into limo- the goethite crystals, it has been possible to fit the dis-
nitic laterite fractions is uncertain (Manceau et al., solution rate to shrinking core/isotropic (Cornell et al.,
2000). The experiments of Kumar et al. (1990, 1993), 1975) or sigmoidal (Schwertmann et al., 1985) kinetic
who studied the leaching of synthetic nickel- and cobalt- models. Sigmoidal leaching kinetics was also noted by
doped goethite samples in mixtures of sulphuric and Surana and Warren (1969) for some natural goethite
sulphurous acids, suggested that the incorporation of samples. The ratio of dissolution rates in 2 M perchloric
cobalt into the goethite structure is favoured over nickel acid, sulphuric acid and hydrochloric acid was 1:5:20
and that surface-induced precipitation of nickel is pre- and the activation energies for dissolution were 74.6,
ferred over structural incorporation, however, this is at 83.4 and 94.3 kJ mol− 1, respectively.
odds with other findings (e.g. Singh et al., 2002). It does It was found that both increasing the ionic strength of
appear though, that the cobalt oxidation state in sub- the leach liquor, through the addition of NaNO3 or
stituted goethite is determined by the conditions of for- NaCl, and increasing the (hydrochloric) acid concentra-
mation (Pozas et al., 2004) although Kumar et al. (1990, tion, increased the rate of iron dissolution (Cornell et al.,
1993) suggested a preference for the divalent state. It is 1976). These authors noted “it is probable that both
well known that manganese and iron generally do not dissolution mechanisms, i.e. attack by H+ assisted by
form solid solutions, but rather precipitate as distinct Cl−, and attack by H+ alone, operate during dissolution
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 39
of goethite by hydrochloric acid, but the former mech- was affected by the amounts of Fe or Mg substituted
anism is the more effective and so outweighs the other”. for Al in the octahedral position. The dissolution rate, as
This mechanism appears consistent with their experi- indicated by the half time of dissolution (in hours), t1/2,
mental data and with suggestions by Surana and Warren depended on the degree of substitution of iron or mag-
(1969), Sidhu et al. (1981) and Chander (1982) that the nesium for octahedrally coordinated aluminium and fol-
anion A−, from the acid HA, complexes with goethite lowed the relationship given in the following expression:
and promotes dissolution.
The effect of ionic substitution for iron in the goethite ln t1=2 ¼ 3:95−1:96 FeVI −2:30 MgVI ð1Þ
lattice also affects its dissolution. Substitution of iron
with aluminium and chromium stabilise goethite against In this instance, the effect of iron and magnesium are
proton attack (Schwertmann 1991). In comparison, Lim- slightly different. A subsequent study similarly found
Nunez and Gilkes (1987) reported that unsubstituted that the decomposition rate of the clay structure in-
and chromium-containing synthetic goethite samples creased with octahedral iron content and the total octahe-
had higher activation energies for acid dissolution (84– dral substitution of iron and magnesium for aluminium
126 kJ mol− 1) than did aluminium-, nickel-, cobalt- and (Komadel et al., 1990).
manganese-containing goethites (42–75 kJ mol− 1). The rate limiting step for smectites such as nontronite
On the basis of unit surface area, chromium-containing and hectorite however, appears to be the breaking of
goethites dissolved at about one tenth the rate of un- bonds to oxygen atoms that connect the octahedral and
substituted, nickel- and aluminium-containing goethites tetrahedral sheets (Bickmore et al., 2001). This is
whereas cobalt- and manganese-containing goethites consistent with an edge attack mechanism (i.e. proton
dissolved at about twice this rate. attack at the edges of layers) for smectites that domi-
nates compared with the gallery access mechanism (i.e.
3.2. Smectites proton attack through the ditrigonal cavities of the basal
surfaces) (Linssen et al., 2002). Furthermore, the smec-
Borchardt (1989) noted that “Selective dissolution of tite dissolution rate is proportional to the concentration
smectites with acid resulted in (i) replacement of ex- of protons that are adsorbed on the reactive edge surface
changeable cations with H3O+, followed by (ii) removal (Amran and Ganor 2005). A schematic comparison of
of octahedral Al, Mg and Fe, then (iii) removal of edge attack and gallery access can be found elsewhere
tetrahedral Si and Al”. This sequence seems to have (Kaviratna and Pinnavaia 1994). For 2:1 type clay
been confirmed by Madejova et al. (1998) who ex- minerals the substitution of AlO4 for SiO4 in the tetra-
amined the leaching of nontronite in 6 N hydrochloric hedral sheets is an important factor in determining
acid at 35 °C, using infrared spectroscopy. Spectra leachability (e.g. Okada et al., 2005). The leaching of
exhibited “a gradual decrease in the intensities of the AlO4 from these sheets opens up other pathways for acid
bands related to octahedral Fe together with a shift of the attack on the octahedral sheets and interlayers by both
Si–O stretching band to higher wavenumbers”. The edge access and gallery access mechanisms. A recent
spectrum of a nontronite sample treated for 30 h showed summary of results pertaining to the chemical modifica-
the expected bands of amorphous silica and the char- tion of smectites can be found elsewhere (Komadel
acteristic bands of kaolinite. The smectite layers were 2003) while the study of porous solids obtained by the
leached by acid at a faster rate than those of kaolinite, mainly hydrochloric acid treatment of clay minerals has
resulting in a product containing mainly kaolinite. It has been a topic of recent interest (e.g. Balci 1999; Prieto
been suggested that nontronite is a gelatinising mineral et al., 1999; Linssen et al., 2002; Temuujin et al., 2003).
undergoing congruent dissolution with complete
decomposition of the silicate structure and dissolution 3.3. Serpentine minerals
of the metal cations (Terry 1983). Recent evidence also
supports the congruent dissolution of smectite (viz. Serpentine minerals dissolve by partial decomposi-
montmorillonite) at pH between 2 and 3 (Metz et al., tion of the silicate structure, in which the metal cations
2005). However, the complete disruption of the crystal- are leached without appreciable release of silica. This
line structure of clay minerals is not necessary to pro- behaviour is known as incongruent dissolution (Lin and
duce amorphous silica (Temuujin et al., 2006). Clemency 1981; Kosuge et al., 1995; Jurinski and
Cicel and Novak (1977) and Novak and Cicel (1978) Rimstidt 2001). It is therefore expected that the silica in
both also reported that the dissolution of smectites (in- serpentine and smectite clay minerals behaves some-
cluding nontronite), in 6 N hydrochloric acid at 96 °C, what differently upon atmospheric acid leaching.
40 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
The amount of silica that enters solution during ser- there are many examples of this kind of test work. The
pentine dissolution has been suggested to depend on the data indicate that nickel is more readily leached from
magnesium extraction. Queneau and Berthold (1986) clay-like (i.e. smectite, saprolite) ores than limonitic (i.e.
noted that it is important not to extract more than 70% of goethite) ores (Canterford 1978a, 1978b, 1979; Griffin
the magnesium in a magnesium silicate lest the “back- et al., 2002). Typical initial acid additions of over
bone of the magnesium silicate molecule break apart, 700 kg/t dry ore and sometimes more than 1000 kg/t dry
deluging the circuit with soluble silicon”. However, it ore are required to achieve high nickel extractions,
has been shown that acid-treated products from anti- ca. 90%, while increasing the pulp density and
gorite may retain the morphology of the original ore maintaining the same acid to ore ratio is also effective
and that only around 5% MgO is necessary to stabilise (Canterford 1979) because the leach liquor has higher
the micropore structure that develops during leaching free acidity.
(Kosuge et al., 1995).
Rice and Strong (1974a) examined serpentine (garni- 3.4.1. Goethitic laterites
erite) dissolution under optimum conditions (4 M hydro- Where nickel is contained within the goethite grains,
chloric acid, 70 °C, 1 h) for the removal of “structural extraction requires complete dissolution of the grain
OH water”, and proposed the following dissolution (Canterford 1979; Chander 1982; Senanayake and Das
mechanism on the basis of spectroscopic analysis of the 2004). Particle size is also important to the leach kinetics
leach residues. The hydroxyl bonds that hold the octa- of goethite as recently demonstrated by Aaltonen et al.
hedral brucite layer and the tetrahedral silica layers (2003). The extent of substitution and crystallinity of
together are removed, allowing rupture of the weak goethite however, is also known to impact upon the
Mg–O bonds and hence removal of nickel and magne- leaching kinetics (Kumar et al., 1990).
sium. In contrast, the stronger Si–O bonds remain intact The requirement to completely leach goethite to
in the silicate layer so that the total dissolution of the release all of the nickel means that the extractions of
serpentine is not required for complete nickel extraction nickel and iron are strongly correlated for limonitic
(Rice and Strong 1974a). According to this mechanism, ores (Chander 1982; Das et al., 1997). Similarly, it
the Ni2+ and Fe2+ from the octahedral layer pass into has been found that the solubilisation of manganese
solution as chlorides, leaving behind a hydrated silica and cobalt mirrors each other, however, both are ex-
residue (Strong 1978, p 270). Maximum nickel extrac- tracted at a greater rate than the nickel (Canterford
tion from the serpentine occurs when the brucite layer is 1986).
removed, indicating that the nickel is octahedrally co-
ordinated (Strong 1978, p 231). Extraction of nickel, 3.4.2. Hematitic laterites
magnesium or iron from a serpentine ore appears to be Greek laterites contain some of the iron as hematite
diffusion controlled, since plots of ‘fraction of reaction rather than goethite. This permits the leaching of nickel
completed’, α, versus square root of time are linear, under conditions mild enough to avoid the high acid
although two linear regions are present in the plots consumption associated with substantial dissolution of
(Strong 1978, p 134). Similarly Rinn and Fetting (1982) iron. A study by Panagiotopoulos and Kontopoulos
concluded that the acid must pass through a porous (1988) showed that high nickel extraction could be ob-
“silica” layer to the un-reacted serpentine. Under the tained during simulated three-stage (90 min each)
conditions employed by the latter authors, the leaching counter-current leaching experiments with an overall
rates for nickel, iron and magnesium were nearly the acid consumption of up to ∼ 500 kg/t ore producing an
same once the “silica” layer had formed. iron to nickel ratio in the liquor of 7.5. Adjustment of the
Similar to clay minerals, the production of high- acid strength and pulp density enabled Ni/Co recoveries
grade silica from other serpentine minerals by leaching to be optimised and iron extraction to be reduced. In
with hydrochloric acid has attracted much interest (e.g. contrast, a six-stage, co-current extraction was less
Petrovski et al., 1987; Taubert 2000; Yang et al., 2003; efficient in controlling iron and the acid consumption
Pietriková et al., 2004). increased to 650–850 kg/t (or 80–100 kg/kg Ni) though
still with high nickel extraction (Kontopoulos 1991).
3.4. Reactivity of various laterite ores A similar conclusion was reached by Panagiotopoulos
et al. (1986). Two- or three-stage counter-current leaching
The use of sulphuric acid to leach different laterite (compared with single stage leaching) of Greek ser-
ore types containing a blend of the above minerals under pentinitic laterites reduced the acid consumption from
AL conditions has been studied for several decades and 1600 kg/t ore (75 kg/kg Ni) to 650 kg/t ore (39 kg/kg Ni)
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 41
without affecting nickel (and cobalt) recovery. Work by to AL with sulphuric acid. The extensive studies of
Halikia (1991) indicated that mass transport through a Canterford (1978a, 1978b, 1979, 1986) also confirm
boundary layer was not the rate-determining step but that such variability, including for samples from within the
nickel leaching was controlled by a chemical mechanism. same ore body. Curlook (2002a) found that leaching
highly serpentinised samples at 80–100 °C, at pulp
3.4.3. Saprolitic ores densities of 15–33% and acid addition of 800–1000 kg/t
The literature that considers the acid extraction dry ore, gave extractions of N90% nickel within an hour.
(under AL conditions) of saprolitic, serpentinitic and At lower temperatures, using higher pulp densities with
garnieritic materials is extensive. Almost twenty articles the same acid to ore ratio, or when using partially-
have been published by Hirasawa and co-workers serpentinised ores, containing b30% MgO, longer times
alone (e.g. Hirasawa and Horita 1987), and therefore were required to achieve similar extractions. Pulping the
only selected examples will be considered in this ore in seawater or freshwater had minimal effect on the
discussion. subsequent nickel extraction.
Serpentine ores are compositionally variable, and the
effect is apparent from the studies of Panagiotopoulos 4. Strategies to improve nickel (and cobalt) extraction
et al. (1986) who reported an acid consumption of
1600 kg/t dry ore for Greek serpentine ore whereas for a Various strategies have been examined to increase
Spanish serpentine, an acid consumption of 780 kg/t dry the recovery of nickel by AL or its selectivity over iron
ore was found (Becerril and Rodriguez 1975). Though to decrease the consumption of acid. These include
focused upon the affect of various parameters upon increasing temperature or leaching time, controlling
extractions, the study of Hirasawa and Horita (1987) redox potential, adding catalysts or pre-treatment to
found that the leach residues consisted mainly of amor- change mineral phases.
phous silica and suggested that this was an excellent raw
material for the production of silicon carbide; this was 4.1. Increasing temperature or leaching time
subsequently demonstrated by Cheng and Hsu (2006). It
was also noted that leaching conducted in “sulphuric Higher temperatures improve the nickel extraction
acid containing magnesium ions” had no effect on the kinetics for sulphuric acid-based AL (Weston, 1974a;
extraction of nickel, iron and magnesium under normal Canterford 1978a; Griffin et al., 2002). However, it has
conditions. While serpentine minerals are leached rela- been shown that the difference in nickel extractions
tively easily, other minerals present in saprolite ores at different temperatures was reduced with extended
such as magnetite/maghemite and chromite, remain leach times and on this basis, Canterford (1978a)
relatively untouched in hydrochloric or sulphuric acid, indicated that “it may be economically and/or tech-
even after long periods of extraction (Rice and Strong nologically appropriate to leach at 65 °C for a longer
1974a,b; Canterford 1986). time than to leach at reflux for a limited time”. Ac-
It is reported that grinding to mechanically activate cordingly, AL processes have been developed at tem-
serpentine minerals can have a significant positive effect peratures near reflux or at ambient temperatures over
upon subsequent leaching (e.g. Suquet 1989; Kim and extended periods of time in heap leaching, as discussed
Chung 2002; Yang et al., 2006). In contrast, particle size later.
has little effect upon the leaching because the nickel is
loosely bound within the octahedral brucite layer and, 4.2. Redox-controlled leaching
unless conditions are sufficiently corrosive to cause
decomposition to silica, the structure of the “clay” does The use of reducing agents to promote the dissolution
not change markedly (Canterford 1979). For minerals of iron oxides is well known and includes sulphur
containing significant amounts of silica a judicious dioxide (e.g. Warren and Hay 1975; Kumar et al., 1990,
choice of leaching conditions is required to prevent the 1993; Kumar 1994), cuprous ions (e.g. Warren and Hay
re-adsorption of the nickel by (re-precipitated) amor- 1975; Byerley et al., 1979; Lu and Muir 1988; Das et al.,
phous silica. 1997) and iron(II) complexes (e.g. Suter et al., 1991).
Curlook (2002a, 2002b, 2004) examined a series of However, the application of reductive sulphuric acid
highly serpentinised saprolitic components that are too leaching to treat limonitic ores dates back to the patent
high in magnesium (N15%) to be suitable for direct of Hayward (1952). Reductive leaching using organic
HPAL treatment. Saprolite ores, even of similar com- acids is discussed in Part II of this review (McDonald
position, can yield very different results when subjected and Whittington, in press).
42 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
It is generally accepted that the mechanism of iron other studies have suggested that this is promoted by
oxide dissolution in an acid involves a number of key the presence of ferrous iron (Tindall and Muir, 1996;
steps: Senanayake and Das, 2004). However, in these ap-
proaches there is a need to control SO2 losses and
Surface protonation ├s OFeIII O þ Hþ ↔├s OFeIII OH ð2aÞ emissions to the atmosphere. To overcome this problem,
├s OFeIII OH þ Hþ ↔├s OFeIII þ H2 O ð2bÞ a recent study examined the electrochemical oxidation
of sulphur dioxide to dithionite in an acid environment
Desorption ├s OFeIII OH þ Hþ ↔├s OH þ ðFeIII OHÞ2þ : ð3Þ and the subsequent leaching of limonitic and saprolitic
laterites using the dithionite as a reductant (Lee et al.,
In the presence of reducing agents (e.g. Fe2+ or 2005). Nickel extractions of 50–75% were obtained
+
Cu ) electron transfer at the oxide surface produces a over 90–120 min using low current density throughout
Fe(II) oxide species that is more readily attacked by the leach to minimise power consumption.
acid: Control of the redox potential also features in the
recent inventions of Arroyo and Neudorf (2001, 2002,
Electron transfer ├s OFeIII OH þ Fe2þ ðCuþ Þ↔├s OFeII OH þ Fe3þ ðCu2þ Þ 2004) whereby a concentrated mineral acid is used to
ð4Þ leach iron and nickel from a high manganese (0.73%),
high chromium (1.52%) limonite ore in the presence of a
Desorption ├s OFeII OH þ Hþ ↔├s OH þ ðFeII OHÞþ : ð5Þ reducing agent and at temperatures up to 95 °C. In this
case, the redox potential is only maintained between 900
Similarly, it has been postulated that a protonated and 1000 mV (versus SHE), by use of small amounts of
SO2 species enables electron transfer to occur at the sulphur dioxide, to minimise the production of ferrous
oxide surface (Kumar et al., 1993; Senanayake 2003). ion, but reduce the manganese minerals and optimise
The use of hydrogen sulphide for the reductive cobalt extraction. The leach liquors typically contained
leaching of limonitic ores with sulphuric acid was about 80 g/L Fe(III).
proposed by Glaum et al. (1977). In this process all of
the nickel and iron could be solubilised or nickel sul- 4.3. Addition of salts
phide could be precipitated out in situ, leaving an iron-
containing solution that could subsequently be decom- The addition of various salts has been noted by
posed to hematite and sulphur dioxide. several groups to enhance the AL of nickel laterites. For
Hatch and Dunn (1983) described an AL process for example, Weston (1974a) noted that the addition of
high-magnesium ore for which the pH and the redox sodium chloride to the leach liquor at levels up to 45 kg
potential were maintained in the ranges 1.5–3.0 and per tonne ore (corresponding to 24 g/L NaCl) increased
200–400 mV (versus SCE), respectively. The main nickel recovery. Chloride salt-assisted leaching was
benefit was significantly increased nickel extraction at also reported for limonite due to complexation of
low Eh together with lower iron extraction by employ- iron with chloride ion (Cornell et al., 1976; Chander
ing lower solution acidity. Atmospheric leaching at 1982). Along similar lines, Hirasawa and Horita (1987)
85 °C for 4 h with acidic HPAL leach liquor resulted in reported that fluoride rather than chloride salts en-
an overall nickel extraction of 93%. hanced the leaching of a New Caledonian garni-
Although the addition of sulphur dioxide during erite ore though this may be due to the formation of
leaching has been reported to accelerate the AL of fluorosilicates.
lateritic ores (e.g. Weston 1974b; Subramanian and
Glaum 1980) or synthetic goethites (Kumar et al., 1990, 4.4. Effects of fine grinding
1993; Kumar 1994), only recently have detailed studies
been published (Das et al., 1997; Senanayake and Das The beneficial effect of attritioning a nickel laterite ore
2004). When the redox potential was lowered from an upon atmospheric leaching was indicated by Canterford
Eh value of 840 mV to 560 mV (versus Ag/AgCl) by (1978b), and is the subject of an invention by Aaltonen
continuously bubbling sulphur dioxide through an acid et al. (2003). Data presented to support the patent indicate
solution at 90 °C, the nickel (and iron) extracted from a a significant increase in the rates of nickel and cobalt
limonite ore after 6 h increased from about 40% to 85%. extraction from a limonite sample at 80 °C if the particle
Similarly, there was preferential acid extraction of cobalt size is reduced from 36 μm to below 5 μm.
from limonite ores in the presence of aqueous sulphur The enhancement of nickel (and magnesium) extrac-
dioxide (Kanungo et al., 1988; Das et al., 1997) and tion by sulphuric and hydrochloric acid solutions from
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 43
serpentine minerals after mechanical activation has been The amount of sulphuric acid used in pugging depends
investigated by several groups (Sanchez et al., 1997; upon the ore type; the higher the magnesium content, the
Zhang et al., 1997; Kim and Chung 2002). Without greater the acid requirement. Small amounts of additives
mechanical activation, acid leaching to obtain amor- such as sodium chloride, potassium chloride, sodium
phous silica from serpentine requires a very high acid sulphate and magnesium sulphate may also promote the
concentration and relatively high temperatures over sulphation of nickel. The optimum sulphation tempera-
80 °C (Girgis and Mourad 1976; Petrovski et al., 1987). ture, however, depends primarily upon the magnesium
Dry grinding of a garnierite ore induced structural content of the ore (Canterford, 1979); a careful balance
change, converting the serpentine from a crystalline to exists between magnesium content, nickel extraction,
amorphous state while quartz and magnetite remain selectivity for nickel over iron, roasting temperature and
crystalline. About 80% magnesium and nickel were acid consumption.
extracted at room temperature though short grinding The treatment of moist lateritic ore with concentrated
times (~ 15 min) were recommended to suppress silicon sulphuric acid and drying of the mixture at a temperature
extraction (Sanchez et al., 1997). From the small scale between 100 °C and 210 °C before water leaching have
laboratory work of Zhang et al. (1997), more than 90% been described by Bailey (1959) and Hansen et al.
magnesium and 70% silicon were extracted into 1 N (1978). However, this requires substantial energy to
hydrochloric or sulphuric acid after grinding for 4 h remove the water and leaching resulted in relatively high
whereas no significant extraction occurred for the un- acid consumption and iron dissolution.
ground sample. Among the magnesium silicates, talc is In a recent patent, rather than drying or roasting the
particularly refractory to acid leaching even at 150 °C ore/acid mixture, Neudorf (2006) allows the “pug” to
(Okada et al., 2003, 2005). Grinding to increase the react, raising the temperature to around 140 °C, and cure
surface area and more particularly amorphatize the talc for sufficient time as to allow substantial reaction. After
structure, is required to achieve high-magnesium extrac- curing, the pug is ground, slurried and leached at 95–
tion (Sanchez et al., 1996; Temuujin et al., 2002; Yang 100 °C, in the presence of an iron-bearing “seed”, for
et al., 2006). Fortunately nickel is rarely associated with sufficient time, typically 12 to 48 h, to dissolve most of
talc in significant concentrations. the nickel and cobalt but leave most of the iron in the
Some studies have shown that grinding does not residue. This invention forms the basis for Skye Re-
significantly enhance the leaching kinetics of serpentine sources proprietary Sulphation Atmospheric Leach pro-
ores and can be detrimental to downstream processing cess. Rather than employing an appropriate limonite/
(Gjelsvik and Torgersen 1983; Chen et al., 2000; Griffin et saprolite ore blend, pilot work on this process involved
al., 2002). Clearly, crystallinity and the degree of pugging of a limonite/acid mixture and subsequent
aluminium substitution also have an effect. Gjelsvik and grinding of the cured pug with crushed saprolite to
Torgersen (1983) suggested that the grain size is kept prepare the leach slurry (Verbaan et al., 2007). The
above 100 μm to produce a residue that is easily washed process was acknowledged to be robust and resulted in
whilst O'Neill (1978) noted that coarser silicate ore leach extractions of 87% nickel and 88% cobalt for a
resulted in slightly lower nickel extraction but the residue sulphuric acid addition of 600 kg/t dry ore.
had markedly better settling properties than that from A method referred to as sulphuric acid acidolysis and
finely ground ore. The complete leaching of serpentine water leaching (SAWL) (Xu et al., 2005) combines
particles can leave amorphous silica that still retains the elements of several of the inventions described above.
morphology of the original particle (Chen et al., 2000). Sulphuric acid is added to a pulp of ore and water and
the product then either oven dried or air cured, or aged,
4.5. Sulphation of laterite ores to improve leach selectivity prior to leaching. However, the optimal conditions for
the ore required ageing of the sulphated mixture at
Several processes have been reported where limoni- ambient temperature for 3–4 days. Although this pro-
tic laterite ore is mixed with concentrated sulphuric acid cess appears to be similar to the invention of Neudorf
in the presence of limited water to sulphate the iron and (2006), high-iron extractions would seem to be a sig-
nickel, and the mixture roasted at temperatures between nificant drawback.
500 °C and 725 °C to convert ferric sulphate to hematite
and insoluble basic iron sulphates (White and White, 4.6. Roasting pre-treatments
1963; Zubryckyj et al., 1965, 1966; Canterford 1979;
Afenya, 1982; Kanungo, 1987; Kar et al., 2000; Swamy The roasting of laterite ores prior to acid leaching has
et al., 2003); thereafter the calcine is leached in water. generally not found common acceptance with industry
44 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
owing to the high costs of drying the ores and the leached iron exists in the ferrous state. A method em-
development of more economical acid leaching pro- ploying hydrogen peroxide to produce AL liquor with a
cesses. However, it is worth noting the various roasting lower concentration of iron was patented by Burkin and
pre-treatment methods and phase changes produced. Monhemius (1981) claiming over 90% less iron was
The use of sulphur dioxide for sulphation roasting at leached.
around 650–750 °C was carried out by Canterford
(1979; 1996) on a range of Australian nickel laterites. 5. Two-stage leaching with neutralisation processes
The optimum nickel sulphation temperature decreased
with increasing magnesium content but the selectivity 5.1. Introduction
for nickel versus iron dissolution increased as the
roasting temperature increased. Other factors such as % Reactive nickel laterite ores with high-magnesia
SO2 in the roasting atmosphere, particle size and content can be used in a second leaching stage to neu-
magnesium content of the ore and addition of sodium tralise acidic liquors produced by the HPAL or AL of
chloride were found to affect nickel recovery and ores with low-magnesia content. Alternatively, acid can
selectivity. Application of a similar process to several be used in a first stage to leach magnesium and pre-
Indian laterites also demonstrated high selective extrac- condition the ore prior to HPAL processing. Such subtle
tion of nickel after roasting at 700 °C that was strongly variations constitute the basis of several patented two-
influenced by the partial pressures of SO2 and O2 and stage leaching processes.
the addition of metal salts (Kar and Swamy, 2001). An early example of a two-stage atmospheric
Simply roasting in air to convert goethite to hematite leaching method for nickel laterites was demonstrated
in limonitic ores has been demonstrated by several by Garingarao and Palad (1975). The recycling of AL
groups to be beneficial to the AL of nickel and cobalt liquor to treat fresh ore could be performed with high
(Kontopoulos 1981; Sukla and Das 1986; Sukla and Das nickel extraction efficiency, and by employing an excess
1987; Sukla et al., 1989). For saprolitic ores, roasting of the ore, reduce the free acid level and precipitate most
enhances the reactivity of serpentine minerals as dis- of the iron.
cussed in the next section. However, Canterford (1979) Niche two-stage leaching applications also exist. A
and Panagiotopoulos et al. (1986) noted that roasting in recent example is the novel process proposed for the co-
air could have a detrimental effect on nickel recovery. treatment of nickel sulphide and laterite ores that may
Various methods of reduction roasting have been occur in close proximity (Liu et al., 2006). In this pro-
claimed to promote and/or improve the selectivity of cess, the leaching of a nickel laterite ore generates a
subsequent acid leaching. These include a wide range of pregnant leach solution containing more than 10–30 g/L
reducing agents such as iron powder (Shirane et al., Fe(III) that is used for the leaching nickel sulphide ore
1983; Kawahara et al., 1987), CO/CO2/H2 gas mixtures either sequentially or simultaneously. Saprolite ore can
(Stevens et al., 1975; Bakker et al., 1977; Bakker and then be used for neutralisation of the product liquor and
Sridhar 1978), pyrite additive and CO/CO2 gas mixtures precipitation of iron.
(Borbely et al., 1974), CO/CO2 gas mixtures (O'Neill, Perhaps the best known example of two-stage leaching
1974; Coldrey and Glen 1975; Purwanto et al., 2003), is the AMAX (or AMAX-COFREMMI) process patented
coal additive (Coldrey and Glen, 1975; Swamy and by Chou et al. (1978) and described at subsequent inter-
Kasipati Rao, 1994), pyrite and coal additive with CO national meetings (e.g. Duyvesteyn et al., 1979). Aspects
gas (Bakker et al., 1977) and hydrogen (Clarkson and of several earlier inventions were subsequently employed
Distin 1976; Apostolidis and Distin 1978). The experi- in the development of both the AMAX Process and the
ments of Canterford (1979) using hydrogen, on the other Enhanced Pressure Acid Leach (EPAL) Process by BHP-
hand, lead to non-selective reduction and he argued Billiton which are outlined in the following sections.
that “selective reduction is in practice very difficult to
achieve” unless the temperature, ore to reductant molar 5.2. Two-stage HPAL–AL leaching: development of the
ratio and reducing potential (viz. gas mixture) are care- AMAX Process
fully controlled.
For a pre-reduced nickel laterite containing 35–50% The inventions of Zundel et al. (1974) and Queneau
iron (as FeO), 1% nickel, 30% silica, about 5% calcium and Chou (1976) were forerunners to the AMAX
plus magnesium (as CaO + MgO) and 7% alumina, the Process (Duyvesteyn et al., 1979). These in turn were
acid requirement for leaching is typically 75–110 kg/t. based upon an earlier Canadian patent (Simons and
However, a significant amount of the proportion of the Carlson, 1961) in which it was proposed that after
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 45
primary leaching of a particular ore, further amounts of recovery of nickel and cobalt from lateritic nickel ores,
the same ore could be employed in the form of a slurry and one that was less sensitive to changes in the ore
to neutralise excess acid remaining in the pregnant grade than other processes. Extensive pilot plant de-
solution. Zundel et al. (1974) used the high-magnesium velopment demonstrated the applicability of the AMAX
fraction of a laterite ore to neutralise the acidic pregnant Process to a broad range of ore compositions from
leach liquor from the HPAL of a low-magnesium ore laterite deposits world-wide (Wicker and Jha 1986).
and then treated the low-magnesium residue with Although this process has not been commercialised, it
HPAL. This neutralisation or pre-conditioning stage has contributed to an improved understanding of many
was carried out at 80–95 °C for sufficient time to features of sulphuric acid laterite leaching and to the
dissolve a substantial amount of the magnesium and longer term development of high-temperature technol-
bring about the hydrolysis of ferric iron and aluminium. ogy. Ultimately, a major failing of the AMAX Process
From examples provided, a four hour conditioning was the high level of iron remaining in the liquor after
period was sufficient to give a final HPAL liquor of pH 2 AL and the poor settling characteristics of the iron
and a residual ore that required almost 30% less acid to precipitate after neutralisation.
yield the same extraction of nickel in HPAL. Queneau
and Chou (1977) noted that following HPAL, the iron 5.3. Improvements to HPAL–AL leaching
and aluminium levels in the autoclave discharge in-
creased with time due to free acid re-dissolving the leach Griffin et al. (2002) noted that the removal of iron
residue. By employing serpentine-type material for par- (and silica) pose problems for all AL processes, whilst
tial neutralisation to pH around 2 the re-dissolution of Motteram et al. (1996) noted that some neutralised
iron and aluminium was greatly inhibited. pulps had unsatisfactory settling characteristics. There-
In the AMAX Process, a key element of the process fore various studies have focused on choosing the best
is that a high-magnesium fraction of the ore is employed neutralisation ore and improving the removal of iron and
to neutralise HPAL pregnant liquor under AL conditions aluminium from solution.
and that the AL residue is recycled with limonite to Studies on Weda Bay ores by Baillie and Cock
HPAL to recover any un-leached nickel. If necessary, (1998) showed that saprolite feed (27% MgO) was most
the high-magnesium fraction may be calcined to render effective compared with high-iron transition zone (8.8%
it more reactive with sulphuric acid and improve its MgO) and low-iron transition zone materials (19%
neutralisation capacity depending upon the magnesium MgO). Curlook (2004) reported that highly serpenti-
availability and the final pH required (Lussiez et al., nised saprolite was very effective for the partial neu-
1985). In contrast, Chou et al. (1978) noted that “high tralisation of HPAL liquor at 100 °C, increasing the
temperature neutralization of the free acid in the liquor pH from 0.9 to 1.6 in 20 min whilst yielding
autoclave itself cannot go beyond pH 1.2 without N 95% nickel (and cobalt) extraction. Clearly ores need
precipitating some nickel from pregnant liquor”. For to be carefully selected for this purpose.
example, they noted that high-temperature neutralisa- The improved removal of aluminium and iron from
tion of laterite leach liquor at 250 °C with magnesia to a leach liquors as alunite, jarosite and hematite was first
pH of 1.6 caused the co-precipitation of about 35% of described by Lowenhaupt et al. (1985). HPAL liquor
the nickel — presumably as insoluble magnesium/ was contacted with either recycled AL residue and/or
nickel sulphate double salts. high-magnesium content ore at 80 °C. The liquor from
Similar patents were later taken out by Koike et al. this step was then raised to a temperature between
(1993) and Murai et al. (2000). The former discusses the 140 °C and 200 °C, to remove the iron and aluminium
benefits of recycling process streams containing sodium dissolved during atmospheric leaching. Recently, Neu-
and ammonium ions, together with recycled AL leach dorf and Huggins (2006) patented the neutralisation of
residue, to enhance nickel recovery during HPAL. The AL liquors with saprolite ore at elevated temperatures,
latter describe the recovery of metal values (Ni, Co, Mn) 150–180 °C, to produce hematite.
as hydroxides and carbonates rather than as sulphides
and carbonates. 5.4. The BHP-Billiton Enhanced HPAL (EPAL) Process
The AMAX Process was referred to by Duyvesteyn
et al. (1979) as “omnivorous”, since it can be simul- The current active interest in AL stems from a patent
taneously and economically applied to low-grade by Duyvesteyn et al. (1996) which in turn refers to the
limonite and high-grade garnierite ores. It was claimed AMAX patent of Chou et al. (1978) as a key work in this
to be the lowest energy consuming process for the area. Subsequently, BHP-Billiton have taken out several
46 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
recent patents (Arroyo and Neudorf 2001, 2002, 2004; 2005). Typically, the nickel extraction from the saprolite
Arroyo et al., 2002) and developed a process for the in the secondary AL step was slow and incomplete
Ravensthorpe Nickel Operation whereby the limonite leading to combined HPAL–AL nickel extractions of
and saprolite ore components are respectively treated by 80–85% after 10–18 h. Increasing the saprolite to limo-
HPAL and AL — designated as Enhanced (H)PAL or nite ratio from 0.61 to 1.25 reduced the final iron con-
EPAL (Reid and Barnett, 2002). It was noted that the AL centration from 25.5 g/L to 5.9 g/L but decreased the
process is “particularly applicable to resources that have overall nickel extraction from 89% to 83% (Liu et al.,
significant saprolite or nontronite components”. 2004).
The original BHP-Billiton invention of Duyvesteyn The recent invention of Liu and Krebs (2006) applies
et al. (1996) described the leaching of high-magnesium EPAL methodology to produce a neutralisation residue
(≥ 5% Mg) ore, with iron and nickel contents of at least composed of both goethite and hematite at saprolite
10% and 0.5%, respectively, using a mineral acid neutralisation leaching temperatures of 95–104 °C after
(≥ 0.25 M) at temperatures of up to 95 °C using heap, 9.5 h. An overall nickel extraction of up to 91% was
vat or agitated-reactor leaching methods. In one em- demonstrated but this appears to require careful selec-
bodiment of the invention, the leach liquor was then tion of the limonite and saprolite fractions for the HPAL
neutralised using fresh ore via counter-current leaching. and AL/SN stages of the process.
The subsequent patents and processes refer primarily to The patent of Neudorf and Huggins (2006) seems to
sulphuric acid leaching and include a step whereby the address the residence time and SN efficiency concerns
saprolite ore is employed at temperatures below the by performing the neutralisation step at 150 °C. Under
slurry boiling point to neutralise the excess acid re- these conditions it was possible to complete the reaction
maining from the primary leaching step, typically from in just 1–2 h and to improve overall nickel extraction by
the limonite ore. This primary leaching step could take as much as 8–9%. Typically, the reaction produced
place under atmospheric conditions (Arroyo and Neu- hematite and reduced the acid requirement. It was
dorf, 2001, 2002, 2004) or under HPAL conditions claimed that the cost of moderate-pressure autoclave
(Arroyo et al., 2002). systems could be comparable to that of AL reactors and
A feature of the BHP-Billiton patents is the focus on would be much simpler to operate and maintain than the
iron removal. Neutralisation with saprolite slurry is carried HPAL autoclaves.
out in the presence of sodium, potassium or ammonium
ions to promote the precipitation of about 80% of the iron 5.5. Comparison of acid requirements for sulphuric
as jarosite in the presence of added seed. Subsequent acid-based processes
periodic addition of limestone slurry, promotes further
jarosite formation in a process referred to as “Induced The operating costs for sulphuric acid leaching
Jarosite Precipitation” (Adams et al., 2004), which is processes for nickel laterite ores are strongly impacted
necessary to “trim” the iron content to produce liquor by the acid requirements. It is important here to dis-
containing b 3 g/L iron. Nickel and cobalt are ultimately tinguish between acid consumption during leaching and
recovered as a mixed hydroxide by addition of magnesia. acid utilised which also includes the amount neutralised
The overall flowsheet is shown in Fig. 1. By comparison, before nickel and cobalt recovery. Rather than quote in
a slightly different flowsheet for the leaching operations kg per tonne of ore treated, the alternative measure of kg
was recently proposed by Lynch et al. (2005) to treat acid per kg of nickel dissolved is perhaps economically
Weda Bay ores whereby the limonite ore is treated by more meaningful.
HPAL and part of the saprolite ore by AL. The combined Depending upon the ore type and blending, acid
leach slurries are then neutralised with fresh saprolite ore. utilisation in the HPAL process is typically between 15
Generically one might refer to this as a HPAL/AL hybrid and 35 kg/kg nickel dissolved where a higher value is
with saprolite neutralisation (SN) or HPAL/AL/SN associated with greater magnesium to nickel ratio of the
process. autoclave feed. Examination of the AL/SN data of Arroyo
It is widely recognised that the jarosite in the leach et al. (2002) and Liu et al. (2005) indicates the following:
residue may decompose slowly and that it consumes
useable acid. Therefore the established method of pre- • Acid utilisation is high when the final liquor has a
cipitating ferric iron as goethite with careful control of high-iron concentration
the redox potential, temperature and pH during second- • Nickel extraction from the saprolite decreases as the
ary leaching and neutralisation was subsequently dem- saprolite to limonite ratio is increased, and the free
onstrated by BHP-Billiton and patented (Liu et al., acid concentration decreases
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
Fig. 1. EPAL pilot plant flowsheet for the processing of limonitic and saprolite feeds (from Adams et al., 2004).
47
48 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
• Overall nickel extraction is improved by using a high- significant amounts of low reactivity hematite together
magnesium, low-iron saprolite ore for neutralisation with goethite. Nickel recoveries of up to 85% were
• Forming goethite rather than jarosite decreases acid obtained in less than 40 days with b50% iron in
utilisation. solution. The sulphuric acid consumption varied from
10.1 to 20.9 kg/kg nickel extracted for the Triada ore
The economics of the EPAL Process for treating both although acid usage varied between 20.8 and 38.0 kg/kg
limonite and saprolite horizons are justified by a lower nickel when residual free acid was taken into account. In
overall acid requirement compared with HPAL. comparison for AL of the same ore in an agitated tank
Although the acid requirement for the saprolite ore the acid usage was 41–72 kg/kg nickel compared
alone can be 30–50 kg/kg nickel depending on the with 27–34 kg/kg nickel for HPAL. The Kastoria ore
magnesium to nickel ratio (Curlook, 2004), when used in was found to be a higher acid consumer due to higher
concert with HPAL of the limonite ore at a low saprolite magnesium content (Agatzini-Leonardou and Zafiratos
to limonite ratio of 0.45, the overall acid requirement 2004). Ore roasting has been demonstrated to improve
becomes significantly lower, around 25 kg/kg nickel. the selectivity for nickel and cobalt over iron during
Similarly, EPAL with the production of goethite or column leaching (Yorio et al., 2006).
goethite/hematite rather than jarosite and higher sapro- The heap leaching invention of Agatzini-Leonardou
lite to limonite ratios around 1.0, had an acid require- and Dimaki (1994b) described the recirculation of
ment of around 30 kg/kg nickel (Liu and Krebs 2006). In leaching solution, through one or more heaps, both
comparison the data provided by Lynch et al. (2005) with and without acid addition between each cycle.
indicate a marginally higher acid requirement of around Leaching was continued until there were no further
35 kg/kg nickel from test work for the Weda Bay increases in the nickel concentration whereas recircula-
project. tion occurred until the acidity fell below a pre-deter-
In summary, the predicted acid requirements for the mined. It was important however to ensure that the
EPAL, HPAL/AL/SN and AL/SN processes can be op- leaching solution did not become saturated in an ele-
timised to 25–35 kg/kg nickel whilst producing a more ment such as aluminium that would subsequently pre-
concentrated nickel leach solution and compare favour- cipitate. A subsequent improvement to this process
ably with a range of 15–35 kg/kg nickel for the existing involving the use of poorer quality process water which
HPAL operations, which may also require more lime for does not effect the extraction of nickel was described
neutralisation. (Agatzini-Leonardou and Dimaki, 2001).
Column leaching tests reported by Duyvesteyn et al.
6. Heap leaching with sulphuric acid (1996) indicated that “clay-like” saprolitic ore had to be
pelletised to prevent the loss of column permeability. This
6.1. Recent developments was also noted by others (e.g. Curlook, 2004) and was due
to magnesium silicate breakdown to produce very fine
Heap leaching of low-grade laterites ores differs in silica that caused the percolation rate to drop to zero. The
principle from the established heap leaching of low- formation of pellets prior to heap leaching is claimed by
grade sulphide ores although in practice both require Duyvesteyn et al. (2001) to be particularly effective for
irrigation with acid, good permeability and extensive ore that has a significant clay content (N 10% w/w). In this
leaching times over several months, at ambient case, the ore is crushed and pelletised by mixing with
temperatures. The main concerns with nickel laterites sulphuric acid having a concentration of at least 100 g/L
are the high acid consumption, potential breakdown of and cured to allow partial dissolution of the ore prior to
the aggregated mineral structures; and the poor heap formation. The recommended amount of acid used
selectivity of nickel over iron and magnesium. for agglomeration was that required to neutralise the
The first serious studies on the column leaching of readily available magnesia. The high permeability of the
nickel laterite ores for possible heap leaching applica- pellets enabled percolation flows of up to 100 L/h/m2 to
tion were conducted on Greek laterite ores; first from the be obtained with good nickel extractions for an acid
Litharakia deposit (Agatzini-Leonardou and Dimaki consumption of less than 500 kg/t dry ore indicating some
1994a), and subsequently the Triada (Agatzini-Leonar- selectivity for nickel over iron.
dou et al., 1997) and Kastoria (Agatzini-Leonardou and It has been claimed that not all laterites can be
Zafiratos 2004) deposits. Selectivity for the leaching satisfactorily agglomerated using just sulphuric acid and
of nickel over iron was demonstrated which in the first that other binders may be required. Jay (2005) suggested
two instances, the ores were limonitic and contained that because a large quantity of the heap is dissolved, it
R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55 49
might be advantageous to bind the laterite to an inert with pregnant liquor recirculation and acid concentration
substrate to enhance percolation. Suitable substrates correction, processes, by Santos de Pontes Pereira and
could include crushed glass, aggregate, gravel or lava De Araújo Gobbo (2007). While open circuit leaching
rock, molded polythene balls in addition to coarse ore extracted marginally more nickel and cobalt over a
particles and screened reject material (e.g. scats). leaching period of 270 days, the sulphuric acid
The source of process water used for agglomeration consumption was significantly higher, 560 kg/t ore.
and leaching has been demonstrated to have a signifi- Although pregnant liquor recirculation with acidity
cant effect upon the leach kinetics (Liu, 2006). The use adjustment was demonstrated to have a slightly lower
of saline water with a total dissolved solids concentra- sulphuric acid consumption, by 30 kg/t, the counter-
tion of between 50 and 150 g/L was recommended in current circuit was proposed to be the best alterna-
combination with sulphuric acid. For the invention of tive since the leaching cycle was substantially shorter,
Purkiss (2004), the addition of sodium metabisulphite 150 days, with sulphuric acid consumption of 280 kg/t.
(5 g/L) to the sulphuric acid (75 g/L) leach solution was A heap height of 4 m was indicated to be optimum.
demonstrated to promote the rapid leaching of cobalt In the first commercial heap leach trial at Çaldağ, the
while 75–80% nickel extraction took around nine heaps were separated; with two for primary leaching
months using bottle rolls testing. ultimately feeding into a third to effect partial neu-
The invention of Miller and Liu (2005) employs tralisation (Purkiss, 2006). The acidity of solution ir-
beneficiation techniques such as scrubbing, screening rigated onto the primary heaps was adjusted to 75 g/L
and classification to separate out a coarse, siliceous low- and fell to around 50 g/L in the underflow. This under-
grade rejects fraction (0.3–0.7% Ni) which is substan- flow was split into a recirculating stream, and one for
tially free from fines and clay mineral, and would which the acidity was further reduced to 5–20 g/L after
otherwise be uneconomic to process by conventional passing through the third heap. However, it was not
treatments. This material, which is typically N75 μm clear whether any iron was rejected from solution during
and b 6 mm, has a high permeability and was suitable for partial neutralisation.
heap leaching without the need to pelletise. Column The amenability of the Çaldağ deposit to heap leaching
tests reported high nickel extractions of 86% and 84% is due to the very low clay content. The dominant nickel-
over 160–192 days with low acid consumptions of containing mineral is goethite while serpentine, quartz,
243 kg/t for limonite rejects and 460 kg/t for saprolite calcite and other iron oxides are also present (Purkiss
rejects, respectively. It was proposed that separate 2006). More details on the mineralogy of the Çaldağ
leaching of these fractions could be tailored to allow deposit and the heap leach operation can be found
maximum nickel recovery from the limonite rejects elsewhere (Çağatay et al., 1980–81; Oxley et al., 2006).
whereas the saprolite rejects would be used for neu- Similarly, four metre test heaps have been operated at
tralisation and to promote iron rejection. A subsequent Minara's Murrin Murrin plant to treat N1 Mt of oversize
patent by Hunter (2006) claimed the separation of the (+1.7 mm), siliceous reject material, referred to as “scats”,
fine ore fraction and utilisation of this fraction to par- that has a low clay content. Extractions of N 80% nickel
tially neutralise the pregnant heap leach solution. An were achieved in less than 180 days. (Minara Resources,
alternative to the process of Miller and Liu (2005) was 2006). Heron Resources have also performed column
described by Rodriguez and Wedderburn (2007) where- leach test work for the Jump-Up Dam project and indicate
by the coarse, siliceous low-grade rejects fraction does that over 70% nickel can be leached from the majority of
not need to be washed to remove any clay component ores over a period of 50 to 150 days (Longworth et al.,
and the heap leach pad can be irrigated with a portion of 2007).
the CCD overflow from a HPAL circuit, rather than
acidified waste liquor. 6.2. Future developments
Panagiotopoulos et al. (1986) and Panagiotopoulos
and Kontopoulos (1988) are amongst several groups that Although at an early stage of maturity, heap leaching
claim a counter-current heap leach process has the would appear to offer the most cost effective method
advantage of lower acid consumption and achieves lower for the extraction of nickel from low-grade nickel
iron and high nickel concentrations in the pregnant laterites. The Çaldağ heap leaching trial operation is
leaching solution, resulting in a cleaner product liquor of expected to expand to full production by 2009 and
lower acidity than from a single heap. The application of produce 20,400 tpa of nickel and 1200 tpa of cobalt in a
counter-current, multi-stage leaching was compared via mixed hydroxide product that will be sold to refineries
column leaching to open circuit leaching and leaching (Irons 2006). The Minara heap leach operation is being
50 R.G. McDonald, B.I. Whittington / Hydrometallurgy 91 (2008) 35–55
expanded over two years to treat 200,000 tpa “scats” tally acceptable waste stream is produced. These two
reject and aims to integrate the heap leach liquors into combined HPAL/AL process variants have been shown at
the existing HPAL plant circuit. pilot scale to be economically viable and form the basis
Other companies including the Yunnan Tin Group, for BHP-Billiton's EPAL Process which has built upon
CVRD Inco and Mirabela Nickel have examined heap earlier experience with the AMAX Process. Variants of
leaching for the treatment of laterite materials. In this process are under consideration by other nickel pro-
Australia, Metallica Minerals are seeking to develop ducers such as Eramet. With the Ravensthorpe Nickel
their Lucky Break and Nornico projects, and Heron Operation expected to be producing mixed hydroxide
Resources their Jump-Up Dam project, to production product in the near future, the true worth of atmospheric
status. Nickel juniors that include GME Resources and leaching for nickel laterite processing will become
Cortona Resources are also considering heap leaching to apparent.
process their deposits. Heap leaching over several months offers low cost
operations for ores having the appropriate mineralogy
7. Summary and conclusions and physical characteristics. Some ores even show some
selectivity for leaching nickel over iron and lower
Nickel is present in various minerals in the limonite, acid consumption compared to AL in stirred tanks. The
smectite and saprolite zones of lateritic ores. The kinetics development of heap leaching for low-grade nickel
and mechanism of leaching of these minerals with sul- laterites is gaining momentum with several trial opera-
phuric acid vary and can be enhanced by modifying the tions expected to expand to full scale production within
leach conditions or by pre-treatment of the ores. Nickel is the next few years.
more readily leached from clay-like (i.e. smectite, The review has highlighted several areas worthy of
saprolite) and high-magnesium ores than from limonitic further study. These include the effects of salt additives
(i.e. goethite) ores. Numerous examples of AL are pre- and Eh upon the chemistry of the AL process; the
sent in the literature which form the basis of several mineralogy of ores for rapid acid neutralisation; and the
processes developed in recent years as an alternative or optimum formation of environmentally desirable and
adjunct to HPAL. A recent novel AL process, developed better handling iron-containing residues. The co-treat-
by Skye Resources, and involving the acid curing of ment of low-grade nickel laterite and sulphide ores
limonite followed by co-leaching with saprolite under mined in close proximity under AL conditions may find
atmospheric conditions warrants further attention. niche applications.
The main advantages of using AL versus HPAL with
sulphuric acid include lower capital (e.g. no expensive Acknowledgements
autoclaves and cheaper materials of construction) and
lower operating costs (e.g. lower energy requirement, less This work was funded by CSIRO Minerals and the
maintenance). When performed in conjunction with Parker Centre for Integrated Hydrometallurgy Solutions.
HPAL, AL effectively consumes acid and partially neu- The authors gratefully acknowledge the assistance of
tralises strongly acidic liquors to leach further nickel from David Muir with the proof reading of this article and for
otherwise reject ore. However, the mineralogy and re- valuable comments, and Evalyn Beaumont and Jill
activity of the ore used for neutralisation is critical for high Rounds for obtaining many of the sources of information.
overall nickel extraction; with high-magnesium saprolite
ores generally performing better. Offsetting this are the References
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