Accepted Manuscript

Selective leaching of nickel and cobalt from limonitic laterite using phosphoric acid: an
alternative for value-added processing of laterite

Guanghui Li, Qun Zhou, Zhongping Zhu, Jun Luo, Mingjun Rao, Zhiwei Peng, Tao
Jiang

PII: S0959-6526(18)31102-8
DOI: 10.1016/j.jclepro.2018.04.083
Reference: JCLP 12664

To appear in: Journal of Cleaner Production

Please cite this article as: Guanghui Li, Qun Zhou, Zhongping Zhu, Jun Luo, Mingjun Rao, Zhiwei Peng,
Tao Jiang, Selective Leaching of Nickel and Cobalt from Limonitic Laterite Using Phosphoric Acid An
Alternative for Value-Added Processing of Laterite, (2018), doi: 10.1016/j.jclepro.2018.04.083

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 ACCEPTED MANUSCRIPT

Graphical Abstract

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 ACCEPTED MANUSCRIPT

A manuscript submitted to Journal of Cleaner Production

Selective leaching of nickel and cobalt from limonitic laterite using

phosphoric acid: an alternative for value-added processing of laterite

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Guanghui Li, Qun Zhou, Zhongping Zhu, Jun Luo*, Mingjun Rao*, Zhiwei Peng, Tao Jiang

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(School of Minerals Processing & Bioengineering, Central South University, Changsha, Hunan

410083, China)

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Abstract
Atmospheric acid leaching has advantages of low energy consumption and

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operating cost, compared with high pressure acid leaching of low-nickel limonitic
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laterites. However, it suffers low nickel recovery, low leaching selectivity of
nickel/cobalt over iron and excessive waste generation. In this work, a new method
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was used for selectively leaching nickel and cobalt, as well as for preparing iron
phosphate intermediate material by atmospheric phosphoric acid leaching of limonitic
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laterite. The results show that 98.7% of nickel and 89.8% of cobalt are leached from
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the calcined limonitic laterite under optimized leaching conditions; meanwhile, 98.3%
of iron is converted into insoluble FePO4·2H2O, resulting in the selective leaching of
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nickel and cobalt over iron. The leaching precipitate of FePO4·2H2O has a purity of
94%, which is expected to be a high-value by-product, providing an extra economic
value. This work presents an alternative for value-added processing of laterite,
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featured by high leaching efficiency of nickel and cobalt without generation of solid
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waste.
Keywords: limonitic laterite; phosphoric acid; atmospheric leaching; selective
leaching; iron phosphate

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1. Introduction
Laterite ore has become the main source of nickel production due to the fast
consumption of nickeliferous sulfide ore. Pyrometallurgical processing is known to be
a widely applied technology for the treatment of laterites (with a portion about 70%)
to produce ferronickel (Maragkos et al., 2009; Warner et al., 2007). In general, for

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producing nickel-rich alloy, saprolitic laterite with high mass ratio of nickel to iron is
disposed via pyrometallurgical processes (Rao et al., 2013). For limonitic laterite

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enriched with iron oxides and relatively high content of cobalt, acid leaching process
is more favorable (Rice, 2016).

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The acid leaching processes of low-nickel-grade laterite can be classified into
two groups, namely high-pressure acid leaching (HPAL) and atmospheric (acid)

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leaching (AL). The HPAL process has advantage of high recovery of nickel and
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cobalt (above 90%), as well as selective leaching of nickel over iron. The ferrous
minerals (especially goethite) are dissolved initially and then ferric ions precipitate in
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the form of hematite during leaching (McDonald and Whittington, 2008; Rubisov et
al., 2000; Whittington and Muir, 2000). These merits make the process a popular
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option for nickel extraction, but specialized apparatus such as titanium-lined

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autoclaves are required due to the harsh operating conditions including high
temperature and high pressure (250-270 oC, 4-5 MPa) (Guo et al., 2011; McDonald
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and Whittington, 2008). Compared with the HPAL process, the AL process consumes
less energy with lower cost (McDonald and Whittington, 2008); however, it has low
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selectivity of nickel and iron extraction since most of nickel coexists within goethite,
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as the extraction of nickel is accompanied by the iron dissolution (Li et al., 2011; Luo
et al., 2015). To obtain high extraction of nickel, the dissolution of goethite should be
intensified, but it results in excessive acid consumption. Besides, large amounts of
iron species are co-existing in the lixivium, leading to nickel loss and low downstream
separation efficiency (Büyükakinci and Topkaya, 2009; Chang et al., 2010; Liu et al.,
2010; Luo et al., 2010; Wang et al., 2011; Zhu et al., 2010).
To date, sulfuric acid has been extensively used in the industry for extracting

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nickel because of its easy availability and low price. Alternatively, hydrochloric acid
and nitric acid are also applied as leaching agents of laterite because sulfuric acid
cannot be recycled (Astuti et al., 2016). As a relatively strong oxidant, nitric acid can
adequately dissolve valuable metals from laterite ores and completely oxidize ferrous
ions for the further precipitation as hematite (Ma et al., 2013). Compared with sulfuric

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acid, nitric acid and hydrochloric acid leaching are less costly (Rice, 2016). Although
hydrochloric acid and nitric acid leaching are attractive, the difficulty in separating

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nickel and iron has not been fully solved. Moreover, citric acid has also been used to
leach laterite and found to be effective in dissolving nickel within serpentine, but not

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much effective for nickel within goethite (Astuti et al., 2016; Li et al., 2010).
Phosphoric acid was reported to extract cobalt and lithium from the waste

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LiCoO2 successfully (Chen et al., 2017). Over 99% LiCoO2 can be transformed into
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Co3(PO4)2 and Li+ in leaching solution by a single leaching step. Phosphoric acid as
leaching agent was also adopted to separate Sc and Ti from red mud (Deng et al.,
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2017). The results show that phosphoric acid can selectively separate the ions such as
Al3+ and Fe3+ by forming the precipitate of iron and aluminum phosphates, which
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provides a new perspective for the separation of cobalt and nickel from iron. In
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addition, the precipitate of FePO4 can be used to synthesize LiFePO4 (Li et al., 2010)
to reduce the waste generation. However, little has been known about the use of
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phosphoric acid as leaching agent for the treatment of laterite, which might be
ascribed to the fact that phosphoric acid is not as strong as sulfuric acid and
hydrochloric acid.
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In this work, phosphoric acid was utilized as leaching and precipitating agent to
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separate and recover nickel, cobalt and iron from the limonitic laterite. The effects of
phosphoric acid concentration, leaching temperature, time and liquid to solid ratio on
the leaching of nickel, cobalt and iron were investigated. Besides, the precipitate after
leaching was also characterized. Expectedly, nickel and cobalt can be effectively
separated from iron which could be recovered as FePO4·2H2O precipitate during
atmospheric leaching. Phosphoric acid leaching under atmospheric pressure is a

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cleaner process than those with sulfuric acid, hydrochloric acid, nitric acid, etc.,
because it offers the potential of minimizing solid waste.

2. Experimental
2.1 Materials
2.1.1 Limonitic laterite

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The typical limonite-type laterite ore used in this work was from Indonesia.
According to the XRD profile (Fig. 1), the ore mainly consisted of goethite,

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maghemite and gibbsite. According to the chemical composition listed in Table 1, the
laterite was featured by high iron content of 43.95%. The cobalt and nickel contents

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were 0.13% and 1.03%, respectively.
2.1.2 Chemical reagents

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The leaching reagents, involving phosphoric acid (H3PO4) and sulfuric acid
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(H2SO4) provided by Sinopharm Chemical Reagent Co., Ltd, were all of analytical
grade.
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2.2 Methods
2.2.1 Calcination of laterite
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The laterite ore was dried at 105 oC for 120 min, and then ground and sieved
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with a 74-µm standard sieve. The pulverized laterite sample was loaded in a
corundum crucible and then calcined at 400 oC for 60 min in a muffle furnace. After
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calcination, the porcelain boat was taken out and cooled down to room temperature.
The calcined samples were then used for acid leaching.
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2.2.2 Acid leaching

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The dried or calcined laterite sample was leached either by sulfuric or phosphoric
solution. The leaching was performed in a beaker immersed in an electro-thermostatic
water bath. Acidic solution (1, 2, 3 and 4 M) was added into the beaker and heated to
the experimental temperature (20, 40, 60, 80 and 90 oC) in the water bath. Five grams
of pulverized laterite sample was then charged into the solution for leaching, with
stirring rate of 200 rpm. After leaching, the mixture was filtered and washed with
distilled water.

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2.2.3 Characterization
The chemical compositions of solid powdery samples were examined using an
X-ray fluorescence spectrometer (XRF, PANalytical, Axios mAX, Netherlands).
Mineral constituents were determined by an X-ray diffraction (XRD, RIGAKU,
D/Max 2500, Japan with Cu Kα radiation), under the conditions of tube current and

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voltage: 250 mA, 40 kV, scanning range: 10-80° (2θ), step size: 0.02° (2θ) and
scanning speed: 8 °/min. Thermal gravimetric analysis and differential scanning

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calorimetry (TG-DSC, STA 449 C, Netzsch, German) was conducted under the
conditions: temperature range of 30-800 oC, heating speed of 10 oC/min, air

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atmosphere, gas flow rate of 20 mL/min. Nickel and cobalt contents in acidic leachate
were determined using a plasma emission spectrometer (ICP-AES, Icap7400 Radial,

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Thermo Fisher Scientific, USA).
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2.2.4 Assessment indexes
The leaching ratios of Fe, Co and Ni and their corresponding leaching selectivity
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(Ni or Co over Fe) were used to evaluate the leaching process. The leaching ratios of
Fe, Co and Ni were calculated according to Eq. (1):
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ε(M,%)=[(c×V)/(m×α)]×100 (1)
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where ε(M) represents the leaching ratio of Fe, Ni, Co, %; c is the content of Fe, Ni,
Co in acidic lixivium, g/L;V is the lixivium volume, L;
is the content of Fe, Ni, Co
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of the dried or calcined laterite sample, wt.%; m is the mass of sample, g.

Subsequently, the leaching selectivity of Ni or Co over Fe could be obtained by
Eq. (2):
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χ=ε(Ni,Co)/ε(Fe) (2)
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3 Results and Discussion

3.1 Effect of calcination on acid leaching
Our previous studies (Li, et al., 2011; Luo, et al., 2015) reported that only 40–60%
of nickel could be leached from raw laterite by atmospheric leaching with sulfuric
acid. The leaching of nickel, however, could be improved from the calcined laterite in
which the mineralogical composition, porosity and surface area were altered (Li, et al,

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2009). In the present study, the effect of calcination was examined first. Based on the
TG-DSC results of laterite ore in Fig. 2, a temperature of 400 oC (high enough for the
dehydroxylation of goethite) was chosen as the calcining temperature. Subsequently,
the dried or calcined laterite were leached either by sulfuric or phosphoric solution, to
investigate the effects of calcination and acid type on the acid leaching. The leaching

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conditions are: acid concentration of 3 M, leaching temperature of 80 oC, time of 120
min and liquid to solid ratio of 10 g·mL–1. The leaching results are presented in Fig. 3.

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It can be seen in Fig. 3a that the leaching ratios of nickel, cobalt and iron are
63.5%, 57.4% and 46.0% respectively from dried laterite ore in H2SO4 liquor. By

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contrast, after calcination, the leaching of nickel, cobalt and iron from the calcined
laterite increase obviously, and attain 95.9%, 91.4% and 92.4%, respectively. Besides,

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the leaching selectivity of nickel over iron is around 1.0, regardless of sulfuric or
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phosphoric solution, suggesting no selectivity of nickel and iron leaching.
Fig. 3b shows the results of phosphoric acid leaching of dried or calcined laterite.
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The leaching ratios of nickel and cobalt from calcined laterite increased from 48.9%
and 67.6% to 98.4% and 89.7%, respectively. The leaching of iron declined from 49.4%
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to 9.4%, indicating the suppressed leaching of iron. Compared to sulfuric acid

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leaching, good leaching selectivity of nickel and cobalt over iron is obtained during
phosphoric acid leaching, due to low leaching ratio of iron. The ratios of nickel and
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cobalt over iron extraction reach 10.7 and 9.4, respectively, when the laterite is
calcined at 400 oC.
Overall, the calcination improves the leaching of laterite. After calcination, the
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transformation of goethite into poor-crystallized hematite (Fig. 4) is of benefit to the

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dissolution of iron (Liu et al., 2013; Li et al., 2013). Besides, the evaporation of water
from goethite creates voids and increases the surface area of particles (Landers et al.,
2011, 2009; Landers and Gilkes, 2007; Löffler and Mader, 2006; Wang et al., 2011).
By comparing the phosphoric acid leaching of dry laterite and calcined laterite, the
high leaching selectivity of nickel and cobalt over iron suggests that iron precipitation
might accompany its dissolution, which demands further investigation.

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3.2 Leaching behaviors of calcined laterite with H3PO4 solution

3.2.1 Effect of initial phosphoric acid concentration
Phosphoric acid leaching of laterite calcined at 400 oC for 60 min was conducted
with different phosphoric acid concentrations at 80 oC for 120 min with a liquid to
solid ratio of 10 mL·g-1.

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It can be seen from Fig. 5 that the leaching ratio of cobalt increases slowly with
increasing concentration of phosphoric acid and reaches the maximum of 89% at 4 M.

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When the phosphoric acid concentration increases from 1.0 M to 2.0 M, nickel
leaching increases greatly from 38.7% to 89.8%, and reaches 98.5% at 4.0 M. It

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should be noticed that in the 1–2.5 M phosphoric acid , only a small amount of iron
(below 4.2%) was leached. When the phosphoric acid concentration increases to 4.0

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M, the leaching ratio of iron rises sharply to about 75%, which results in the
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unsatisfied leaching selectivity of nickel and cobalt over iron. To ensure the sufficient
leaching of nickel and cobalt on the premise of their leaching selectivity, the optimal
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phosphoric acid concentration is 2.0-3.0 M.

3.2.2 Effect of leaching temperature
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The effect of leaching temperature on the leaching of laterite calcined at 400 oC

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for 60 min is shown in Fig. 6 by fixing the other conditions including leaching time of
180 min, H3PO4 concentration of 3 M, and liquid-solid ratio of 10 mL·g-1.
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Fig. 6 shows that the leaching ratios of different metals are relatively low at
temperature of 25 oC. With the increase of leaching temperature to 90 oC, the leaching
proportion of nickel, cobalt increase rapidly and reach maximum of 98.7% and 89.8%,
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respectively. While the leaching of iron increases initially and then declines, with a
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maximum at 60 oC. This tendency accounts for the high leaching selectively of nickel
and cobalt over iron. The leaching selectivities of nickel and cobalt over iron
extraction are 74.8 and 69.1, respectively, at 90 oC. Overall, the experimental
temperature range of 80–90 oC is optimal for selective leaching of nickel and cobalt.
3.2.3 Effect of leaching time
Effect of leaching time on the leaching of calcined laterite was investigated, and

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the leaching conditions were kept as follows: 3 M phosphoric acid, leaching

temperature of 80 oC and liquid to solid ratio 10:1 mL·g-1.
Fig. 7 shows that leaching of nickel and cobalt increase rapidly within in 60 min,
and then keep almost constant at ~98% and ~90% respectively with further extension
of leaching. Their corresponding leaching selectivities present similar trend along

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with the leaching time. In regard to the leaching of iron, it increases and then
decreases, giving a peak value at about 30 min. The decreasing leaching of iron after

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30 min is attributed to the arising leaching selectivity of nickel and cobalt, which is
beneficial to subsequent separation.

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3.2.4 Effect of liquid to solid ratio
The effect liquid-to-solid ratio on the leaching calcined laterite is shown in Fig. 8,

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under conditions of leaching time of 120 min, H3PO4 concentration of 3 M, and
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leaching temperature of 90 oC.
It can be seen from Fig. 8 that liquid to solid ratio positively affects leaching of
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nickel and cobalt. When the liquid to solid ratio increases from 10 to 12 mL·g-1, there
is a decrease in leaching selectivity of nickel and cobalt over iron. The optimal liquid
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to solid ratio is about 10 mL·g-1.

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3.2.5 Characterization of the precipitate–hydrated iron phosphate

Based on the aforementioned experimental results, the optimal leaching
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conditions could be obtained as follows: phosphoric acid concentration of 2-3 M,

leaching temperature of 80-90 oC, leaching time of 180-240 min and liquid to solid
ratio of 10 mL·g-1. Under these conditions, the leaching ratios of Ni and Co from
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laterite calcined at 400 oC for 60 min reach 98.7% and 89.8%, respectively, and 98.7%
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Fe is remained in the precipitate. Chemical composition and phase of the precipitate

dried at 105 oC for 120 min are shown in Table 2 and Fig. 9, respectively.
The main phase of precipitate is FePO4·2H2O with a purity of about 94%. It
could be used as an intercalation electrode in lithium-ion battery (Li et al., 2010).
FePO4 is an electrode material for batteries in electric vehicles due to its thermal
stability and recyclability. It can also be used in metal manufacturing for improving

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the corrosion resistance (Jegdić et al., 2011). Iron phosphate coatings are used as base
coatings to increase adhesion of iron/steel substrate, and are often used in rustproofing
as well. It should be pointed out that phosphoric acid as leaching agent is more
expensive than sulfuric acid and hydrochloric acid, but the obtained iron phosphate
has higher value for its wide usage.

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3.3 Mechanism on selective leaching of laterite with phosphoric acid
3.3.1 Chemistry of precipitation of metals ions in phosphoric acid solution

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During phosphoric acid leaching, the selective leaching of nickel and cobalt over
iron can be achieved, depending on the precipitation of iron phosphate. To illustrate

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the mechanism of selective leaching, the precipitation pH0 of various metals was
investigated further.

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In the aqueous solution, the ionization of phosphoric acid occurs stepwise as
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follows:
H3PO4⇌ H++H2PO4- Ka1=7.6×10-3 (3)
H2PO4-⇌ H++HPO42-
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Ka2=6.3×10-8 (4)
HPO42-⇌ H++PO43- Ka3=4.4×10–13 (5)
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where Ka1, Ka2 and Ka3 are the ionization equilibrium constants of H3PO4 at 25 oC and
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1 atm.
For phosphate precipitation reaction of bivalent cation:

3M2+ + 2 PO4  = M2+ 3 PO4 

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3- 3-
(6)
2

M2+  PO4  =Ksp

3 2
3-
(7)
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c PO4
1/2
3- K0sp
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c M2+ /C0 
= 3 (8)

K0a1 K0a2 K0a3 cH3 PO4 /C0

c H+ =  
cPO4 /C0
3-
(9)

1/3
K0a1 K0a2 K0a3 cH3 PO4 /C0
pH =-lgC H+ =-lg   (10)
K0sp /c M2+ /C0  
3 1/2

Similarly, for the trivalent cation,

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K0a1 K0a2 K0a3 cH3 PO4 /C0
pH =-lg 


1/3

K0sp /c M3+ /C0 

(11)

The precipitation pH0 is used to evaluate the ability of metal cations combining
with phosphate anion. In general, the smaller the pH0 is, the easier the precipitation of
metal ions is. Based on the Ksp value of different metal phosphate (Table 3), the

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initial precipitation pH0 variation of different metals was calculated by Eqs. (10) and
(11), the results are shown in Figs. 10 and 11. It can be seen in Fig. 10 that

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precipitation pH0 decreases with the raising cation concentration. When the cation
concentration is below 0.1 M, the precipitation pH0 marks an evident decrease with

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the cation concentration increases. This trend slows down at the higher cation
concentration. Besides, the initial precipitation pH0 also decreases as the phosphoric

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acid concentration increases (Fig. 11). The precipitation pH0 of FePO4 is much lower
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than those of other metal phosphates throughout the examined range. It means that the
precipitation of metal ions in phosphoric acid solution can be controlled via regulating
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the pH value of leaching solution.

Fig. 12 presents the measured variation of pH value along with the leaching time
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at different initial phosphoric acid concentration (1, 2, 3, and 4 M). It is observed that
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the pH value of phosphoric acid solution increases sharply and then decreases slightly
as the leaching goes on. Compared with initial precipitation pH0 of FePO4, Ni3(PO4)2,
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Co3(PO4)2 in Figs. 10 and 11, the pH value of phosphoric acid solution is higher than
the initial precipitation pH0 of FePO4 but lower than the initial precipitation pH of
Ni3(PO4)2 and Co3(PO4)2. Hence, the dissolved iron cation is precipitated as FePO4 as
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the leaching time increases, while nickel and cobalt cations remain in the solution.
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3.3.2 Main chemical reactions during H3PO4 leaching process

During the leaching of calcined laterite with phosphoric acid, the main reactions
include dissolution of metal oxides and precipitation of metal cations. Firstly, nickel,
cobalt and iron oxides within laterite react with H3PO4 and form Ni2+, Co2+ and Fe3+
cations in solution (Eqs. (12)-(14)), contributing to the increase of leaching of Ni, Co
and Fe (Fig. 7). These reactions consume H+ from the ionization of H3PO4 (Eq. (3)),

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and pH value of leaching liquor increases. Because the ionization of H3PO4 is

promoted, the H2PO4- concentration in solution increases (Fig. 13), and in turn the
HPO42- concentration rises (Eqs. (15)-(17)). Hence, the PO43- anion concentration
increases (Eq. (5)).
It can be seen from Fig. 12 that the pH value in the solution is 0.8 at leaching

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time of 10 min, the corresponding PO43- concentration is 1.5×10-19 M in solution (Fig.
13). Fig. 7 also shows that the Fe3+ content is 1.3×10-3 M in solution, it means that the

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reaction of Fe3+ cation and PO43- anion is occurred at leaching time of 10 min, and the
Fe3+ cation is precipitated in the form of hydrated iron phosphate (Eq. (18)). However,

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it seems the leaching rate of iron is higher than precipitate rate of Fe3+ cation within
30 min, which results in the increasing leaching of iron. The pH value of liqour is also

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improved (Fig. 12). The increased Fe3+ and PO43- concentrations promote the
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precipitation of iron phosphate and, when the precipitating rate of Fe3+ exceeds its
dissolving rate, the leaching ratio of iron decrease gradually. Furthermore, the
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dissolved Ni2+ and Co2+ will not react with PO3- in liquor within the pH value of
0.7-1.4 (Figs. 10 and 13). Consequently, the selective leaching of nickel and cobalt
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over iron is achieved.

Fe2O3+6H3PO4→2Fe +3H2O+6H2PO4-
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(12)

NiO+2H3PO4→Ni +2H2O+2H2PO4- (13)

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CoO+2H3PO4→Co2++2H2O+2H2PO4- (14)

Fe2O3+H2PO4- →2Fe +H2O+HPO42-

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(15)

NiO+2H2PO4- →Ni +H2O+2HPO42-

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(16)

CoO+2H2PO4- →Co +H2O+2HPO42- (17)

Fe3++PO43-+2H2O→FePO4·2H2O (18)

4. Conclusions
Phosphoric acid was used to effectively utilize limonite laterite via an AL
process. Ni and Co were selectively leached, while iron was recovered in the form of
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FePO4·2H2O. For the phosphoric acid leaching of laterite calcined at 400 oC for 60
min, the optimal leaching conditions are: 3 M phosphoric acid, leaching temperature
of 90 oC, leaching time of 180 min, and liquid-solid ratio of 10 mL·g-1. The leaching
of Ni and Co reached 98.7% and 89.8%, respectively; while 98.7% Fe precipitated in
the residue. Iron oxides within the laterite dissolved in the phosphoric acid solution

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firstly and then Fe3+ combined with PO43- to form FePO4·2H2O, due to the selective
leaching of Ni and Co and the simultaneous precipitation of Fe. The precipitate

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containing about 94% FePO4·2H2O could be used as an intercalation electrode in a
lithium-ion battery and metal manufacturing processes etc.

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Acknowledgements
This work was supported by the National Natural Science Foundation of China

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(No. 51234008) and the Co-Innovation Center for Clean and Efficient Utilization of
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Strategic Metal Mineral Resources.

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Figure and Table Captions

Figures:
Fig. 1. XRD pattern of the limonitic laterite ore.
Fig. 2. TG-DSC results of limonitic laterite ore.
Fig. 3. Comparisons of sulfuric and phosphoric acid leaching of dried laterite with

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calcined laterite.
Fig. 4. XRD pattern of calcined laterite (400 oC, 60 min).

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Fig. 5. Effect of initial phosphoric acid concentration on leaching of calcined laterite.

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Fig. 6. Effect of leaching temperature on the leaching of calcined laterite.
Fig. 7. Effect of leaching time on leaching of calcined laterite.

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Fig. 8. Effect of leaching liquid-to-solid ratio on leaching of calcined laterite.
Fig. 9. XRD pattern of the precipitate.
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Fig. 10. Initial precipitation pH of FePO4, Ni3(PO4)2, Co3(PO4)2 as the function of
Fe3+, Ni2+ and Co2+ concentration (initial phosphoric acid concentration: 3 M).
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Fig. 11. Initial precipitation pH of FePO4, Ni3(PO4)2, Co3(PO4)2 as the function of

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phosphoric acid concentration (suppose that iron, nickel and cobalt are totally
dissolved from the laterite and their corresponding concentrations are 0.89 M,
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0.02M, 0.0025M respectively).

Fig. 12. Variation of pH value with leaching time increases in different initial H3PO4
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concentration (leaching temperature of 80 oC, liquid to solid ratio of 10:1

mL·g-1).
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Fig. 13. Ionization degree of phosphoric acid at different pH (initial phosphoric acid
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concentration: 3 M).

Tables:
Table 1. Chemical composition of laterite ore (wt.%).
Table 2. Chemical composition of precipitate (wt.%).
Table 3. Ksp value of different metal phosphates (Stephen and Stephen, 1963).

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Tables
Table 1. Chemical composition of laterite ore (wt.%)
Fetotal Ni Co MnO2 Al2O3 MgO Cr2O3 SiO2 LOI*

43.95 1.03 0.13 1.25 9.72 0.98 3.25 4.25 15.96

*LOI: Loss on ignition.

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Table 2. Chemical composition of precipitate (wt.%).

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FePO4·2H2O Al2O3 NiO CoO MnO2 MgO Cr2O3 SiO2

94.1 2.93 0.046 0.012 0.46 0.11 0.20 0.96

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Table 3. Ksp value of different metal phosphates (Stephen and Stephen, 1963).
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Phosphate FePO4 Ni3(PO4)2 Co3(PO4)2

Ksp 1.30×10-22 5.00×10-31 2.00×10-35

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Figures

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Fig. 1 XRD pattern of the limonitic laterite ore.

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Fig. 2. TG-DSC results of limonitic laterite ore.
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Fig. 3. Comparisons of sulfuric and phosphoric acid leaching of dried laterite with
calcined laterite.
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Fig. 4. XRD pattern of calcined laterite (400 oC, 60 min).
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Fig. 5. Effect of initial phosphoric acid concentration on leaching of calcined laterite.
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Fig. 6. Effect of leaching temperature on the leaching of calcined laterite.
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Fig. 7. Effect of leaching time on leaching of calcined laterite.
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Fig. 8. Effect of leaching liquid-to-solid ratio on leaching of calcined laterite.
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Fig. 9. XRD pattern of the precipitate.
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Fig. 10. Initial precipitation pH of FePO4, Ni3(PO4)2, Co3(PO4)2 as the function of
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Fe3+, Ni2+ and Co2+ concentration (initial phosphoric acid concentration: 3 M).
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Fig. 11. Initial precipitation pH of FePO4, Ni3(PO4)2, Co3(PO4)2 as the function of
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dissolved from the laterite and their corresponding concentrations are 0.89 M, 0.02M,
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Fig. 12. Variation of pH value with leaching time increases in different initial H3PO4
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Fig. 13. Ionization degree of phosphoric acid at different pH (initial phosphoric acid
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Highlights

Atmospheric leaching of limonitic laterite with phosphoric acid was conducted.

It offers the potential of reducing energy consumption and minimizing solid waste.

Selective leaching of nickel and cobalt over iron can be achieved.

The high-value-added utilization of iron could be attained as well.

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Calcined laterite is more amenable to phosphoric acid leaching.

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