Minerals Engineering 98 (2016) 14–21

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Comparing iron phosphate and hematite precipitation processes for iron

removal from chloride leach solutions
Saviour Masambi, Christie Dorfling ⇑, Steven Bradshaw
Department of Process Engineering, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: The presence of iron in pregnant leach solutions presents significant processing challenges. The removal
Received 16 November 2015 of iron impurities from leach solutions by means of iron phosphate precipitation may be a feasible alter-
Revised 27 June 2016 native to more conventional iron oxide/iron hydroxide precipitation processes. This study compares the
Accepted 2 July 2016
performance of the iron phosphate precipitation process with that of the hematite process at different
Available online 12 July 2016
operating temperatures (40 °C–90 °C), pH conditions (pH 1–pH 3) and seeding measures for the removal
of iron from a chloride leach solution. The extent of iron removal, co-precipitation of nickel and copper,
Keywords:
and solid-liquid separation were used as performance criteria for the comparison.
Hematite
Iron phosphate
Seeded iron phosphate precipitation at pH 1 and 40 °C resulted in 98.8% iron removal with 0.5% nickel
Precipitation and 2.8% copper losses. 99.8% iron removal was achieved with the iron phosphate precipitation process at
pH 1 and 80 °C, but the nickel and copper losses increased to 8.7% and 20.8%, respectively, with the
increase in temperature. Seeded hematite precipitation at pH 1 and 80 °C yielded 99.6% iron removal with
3.5% nickel and 1.7% copper losses. For the hematite process, nickel and copper losses decreased with an
increase in temperature. Increasing the pH yielded higher nickel and copper losses for both processes.
All seeded precipitation experiments produced easily filterable precipitates. Unseeded iron phosphate
precipitates produced at 40 °C and pH 1 were filterable, but increased nickel and copper losses were
observed. Unseeded hematite precipitation resulted in high nickel and copper losses, with the precipi-
tates practically impossible to filter. Iron phosphate precipitates exhibited more favourable settling
characteristics than the precipitate produced with the hematite process.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction and Riveros, 1999). Controlled precipitation of a-goethite in sulphate

In hydrometallurgical processes, iron is commonly removed
from pregnant leach solutions by precipitation as jarosite, goethite
or hematite. The jarosite process is extensively used during iron
removal in zinc hydrometallurgy. The co-precipitation of metal
ions (Zn, Cu, Ni, Mn, Al, Ga and Ge) has been cited as one of the
major weaknesses of the jarosite process (Claassen et al., 2002;
Wang et al., 2011). Furthermore, jarosite compounds are univer-
sally classified as hazardous wastes because of the adverse effects
to the environment and human health (Asokan et al., 2006). The
essential feature of goethite precipitation is that the ferric concen-
tration of the solution should be maintained at approximately 1 g/L.
Goethite is said to be precipitated as either a-goethite in sulphate
systems or b-goethite (akaganeite) in chloride systems. Akaganeite
has been reported to sustain co-precipitation of cations and its
filtration is practically impossible (Cohen et al., 2005; Dutrizac
⇑ Corresponding author.
E-mail address: dorfling@sun.ac.za (C. Dorfling).
systems ensures lesser impurities in the precipitates and its filtration
is easily achievable (Ismael and Carvalho, 2003). Production of large
volumes of goethite has been reported to be an environmental con-
cern (Dutrizac and Riveros, 1999). Hematite (Fe2O3) is the preferred
iron precipitate because it is a stable, high density and more pure
form of iron. These properties of hematite make it easier for disposal
and offer the potential for it to qualify as a by-product; it is used as
starting material in the production of iron and steel, pigments and
ferrites (Riveros and Dutrizac, 1997).
Twidwell et al. (1987) reported the invention of a method for
recovering metal values from mixed aqueous solutions by selective
phosphate precipitation. It was reported that the precipitate pro-
duced was easily separated by conventional solid-liquid filtration
techniques, and that the process was applicable in most systems
(sulphates, chlorides and mixtures of these lixiviants). Because of
its distinctive selectivity towards trivalent metal precipitation over
divalent metal precipitation, phosphate precipitation was sug-
gested to be a suitable iron removal method during the purification
of solutions containing divalent metals such as nickel and copper

http://dx.doi.org/10.1016/j.mineng.2016.07.001
0892-6875/Ó 2016 Elsevier Ltd. All rights reserved.
 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21
(Twidwell et al., 1987). Garole et al. (2012) furthermore reported
that the iron phosphate precipitation process is more efficient
and economical than high temperature hydroxide precipitation
processes characterised by precipitates that are difficult to
separate.
To date, very little information about the phosphate precipita-
tion process for iron removal has been published, and no quantita-
tive comparison of the technical performance of this process and
conventional iron oxide/iron hydroxide processes has been done.
The objective of this study was hence to investigate the iron phos-
phate precipitation process as an alternative iron removal process
for purification of a nickel-copper chloride leach solution. More
specifically, this study compares the performance of the iron phos-
phate precipitation process with that of the commonly used hema-
tite precipitation process in terms of iron removal, the extent of
nickel and copper co-precipitation, and solid-liquid separation.
The work formed part of a project aimed at the development of
a process for copper and nickel recovery from a pregnant leach
solution, with iron removal by precipitation envisaged to be the
first processing step. The pregnant leach solution originates from
a metal production facility that utilises hydrochloric acid leaching
for the dissolution of base metals from a specific feed material.
Given the operational requirements of the upstream leaching
process, the leach solution produced contains approximately 4.6 M
HCl, 45 g/L Fe, 3 g/L Cu and 3 g/L Ni.
1.1. Iron phosphate precipitation
Jenkins et al. (1971) presented an overview of research work
performed to develop a process for phosphate removal from
wastewater by means of precipitation with iron added as iron chlo-
ride salts. The same principle has been applied in hydrometallurgy
for iron removal from leach solutions by means of precipitation
with phosphate addition (Cruz et al., 1980; Garole et al., 2012;
Twidwell et al., 1987).
Cruz et al. (1980) investigated the removal of iron from elec-
trowinning solutions. It was reported that iron(III) phosphate
was precipitated at pH 2 and a temperature of 50 °C. The morphol-
ogy of the iron phosphate was spherites and agglomerates of
spherites. Redissolution of the phosphate precipitate was, how-
ever, observed at a ferric to phosphate ratio higher than 3.15.
Twidwell et al. (1987) reported that the phosphate precipitation
process selectively recovers trivalent metal cations as easily sepa-
rable crystals, making it suitable for purification of sulphate or
chloride solutions containing divalent metal cations such as nickel
and copper. Twidwell et al. (1987) suggested a similar precipita-
tion temperature (60 °C) and pH (pH 2) to those proposed by
Cruz et al. (1980). The findings of Cruz et al. (1980) and Twidwell
et al. (1987) were confirmed by Garole et al. (2012). Garole et al.
(2012) reported that the low co-precipitation of divalent metallic
cations can in part be ascribed to poor adsorption on the precipi-
tated iron phosphate, which exhibited spherical shapes and a low
specific surface area. Typical reaction times recorded ranged from
30 min to 1 h, achieving more than 99% iron removal. Iron phos-
phate precipitation was proposed to proceed according to Eq. (1).
Fe3þ þ PO34 þ 2H2 O $ FePO4  2H2 O ð1Þ
The variation in iron phosphate solubility at 50 °C with pH was
determined by Huang (2001) and reported by Twidwell and
Dahnke (2001). The solubility was reported to decrease linearly
with increasing pH. At pH 0, the solubility is approximately
1050 mg/L; above pH 2 iron phosphate is virtually insoluble.
Robins et al. (1991) reviewed literature on the solubility and
speciation of iron(III) phosphate and concluded that the reported
solubility constants of ferric phosphate dihydrate, which is the
15
more common type of iron(III) phosphate, ranged between
4.57  103 and 2.24  108. The dimorphic nature of iron(III)
phosphate (orthorhombic or monoclinic structure) was the pro-
posed reason for the differences in solubility constants reported
in literature.
Twidwell et al. (1986) reported that conversion of ferric phos-
phate to ferric hydroxide, and therefore regeneration of phosphate,
is possible at moderate temperature (25–50 °C) and high pH (pH
11–pH 12) conditions. Complete conversion with caustic soda
was achieved after two hours reaction time at pH 12 and 50 °C.
Unlike the precipitates produced in a conventional hydroxide pre-
cipitation process, the ferric hydroxide precipitates produced by
the conversion of ferric phosphate filter as easily as ferric phos-
phate and do not contain heavy metals (which presents environ-
mental challenges) because of the purity and morphology
inherited from the ferric phosphate precipitates. The conversion
reaction is shown in Eq. (2).
FePO4 þ 3NaOH $ FeðOHÞ3 þ Na3 PO4 ð2Þ
1.2. Hematite precipitation
Traditionally, hematite precipitation has been reported to be
possible at a temperature greater than 100 °C and under pressure
oxidation of greater than 5 bar (Dutrizac and Monhemius, 1986).
Hematite precipitation proceeds according to Eq. (3).
2Fe3þ þ 3H2 O $ Fe2 O3 þ 6Hþ ð3Þ
Dutrizac and Riveros (1999) investigated the precipitation of
hematite from chloride solutions at temperatures below 100 °C
and ambient pressure mainly by employing seeding. In the absence
of seeding, a reaction time of almost 100 h was required for aka-
ganeite to precipitate and transform to hematite. Tests conducted
at 100 °C yielded hematite after only 2 h of reaction time when
seeded with 15 g/L Fe2O3. It was reported that hematite precipita-
tion occurred via two pathways: the precipitation of akaganeite
(a metastable phase) which then gradually transforms to hematite,
and the direct precipitation of hematite. A combination of both
pathways was suggested to be possible, but the direct formation
of hematite was identified as the more likely pathway in seeded
reactions. Decreasing the temperature to 60 °C did not have an
adverse effect on the iron removal achieved by hematite precipita-
tion. More than 99% of the iron initially in solution was reported to
be in the hematite precipitate.
Cohen et al. (2005) also investigated iron removal by hematite
precipitation. It was reported that pH values below 1 did not signif-
icantly affect filtration rates and ensured almost complete removal
of iron, provided seeding levels were between 10 and 20 g/L. Seeding
had a significant impact on the rate of filtration. Typical filtration
rates averaged 83 mL/min and increased with an increase in
operating temperature and reaction time. Seeding beyond 20 g/L
did not have any further impact on filtration rates. Unseeded
experiments performed at temperatures below 100 °C did,
however, produce precipitates that were not practically possible
to filter; this was attributed to the formation akaganeite instead
of hematite.
2. Experimental
2.1. Materials
Unless stated otherwise, all chemicals were reagent grade
chemicals supplied by Sigma-Aldrich. Synthetic leach solutions
containing 45 g/L iron, 3 g/L nickel and 3 g/L copper were prepared
using iron(II) chloride tetrahydrate, copper chloride, nickel
16 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21
chloride hexahydrate and hydrochloric acid. Oxidation of ferrous to
ferric was achieved by sparging oxygen through the synthetic leach
solution. Neutralisation of the leach solution was achieved through
the addition of sodium hydroxide solution prepared using ACS
reagent grade sodium hydroxide pellets and demineralised water,
while phosphate was introduced in the form of sodium phosphate.
Iron(III) phosphate and iron(III) oxide (purified grade) were used
for seeding of the phosphate precipitation process and the hema-
tite process, respectively.
2.2. Equipment
All precipitation tests were performed in a closed 1.6 L glass
vessel. The reactor was fitted with an overhead mechanical agita-
tion system to drive a PTFE coated dual (axial and radial) impeller
system. For oxidation, oxygen was sparged through a PTFE tube
positioned below the bottom impeller. The temperature of the
solution was maintained within 2 °C of the setpoint temperature
by means of a heating plate with feedback control. pH control
was achieved by a Thermo Scientific Alpha pH 560 controller;
the controller output was a solenoid valve connected to the outlet
of a burette filled with sodium hydroxide, which was gravity fed
into the reactor as required. Sampling was done using syringes
connected to sampling tubes inserted through the reactor lid.
2.3. Experimental design
The hematite process and the iron phosphate process were
compared at different levels of pH and temperature with and with-
out seeding. Experiments were conducted to validate the effect of
the solution pH, the solution temperature and seeding on the pre-
cipitation of iron(III) and the resulting losses of nickel and copper.
A summary of the independent variable levels investigated for both
precipitation processes is presented in Table 1.
2.4. Experimental procedure and sample analysis
Oxidation of ferrous in the synthetic leach solution was
achieved by sparging oxygen through the solution in the agitated
reactor (impeller speed of 600 rpm) at 80 °C until 98% oxidation
had been achieved; the extent of oxidation was verified by means
of titration with potassium dichromate using sodium dipheny-
lamine as indicator. After oxidation, the solution was allowed to
reach the setpoint temperature for the precipitation experiment.
The oxidized solution, containing 4.6 M HCl, was neutralized to
pH 0 using a 15.5 M NaOH solution; subsequently, a 1 M NaOH
standard solution was used to control the pH to the setpoint value.
In the case of iron phosphate precipitation experiments, stoichio-
metric amounts of sodium phosphate were added before attaining
pH 0. For seeded precipitation, seeds were added at pH 0 or at pH
0.5 for tests performed at pH 1 and above. For both hematite and
iron phosphate experiments, the starting time for seeded and
unseeded precipitation experiments was noted upon attaining
the desired pH.
Solution samples were taken at the sampling times specified in
Table 1; the duration of the experiment was 2 h. The solution
Table 1
Experimental planning and variables investigated for the respective precipitation
processes.
Variable Phosphate Hematite
Solution pH 0, 1, 2, 3 0, 1, 2, 3
Solution temperature (°C) 40, 60, 80 60, 80
Seeding (g) 0, 30 0, 30
Sampling times (min) 0, 10, 20, 30, 60, 120 0, 10, 20, 30, 60, 120
samples were filtered using 0.45 lm syringe filters. The samples
were then sealed and stored in 15 mL centrifuge tubes for analysis
using inductively coupled plasma optical emission spectrometry
(ICP-OES). The concentrations of nickel, copper, iron, sodium and
phosphorous were analysed by this method.
For the purpose of precipitate characterisation, 200 mL of the
slurry were collected at the end of the experiment and filtered
using a Büchner funnel with quantitative filter paper. The filtration
rate was determined by measuring the time required for filtration
to be completed. The precipitates collected in the filter cake were
washed with deionised water to ensure that nickel and copper
were not mechanically trapped in the precipitate, where after the
precipitate was left to dry for 20 h at 40 °C. Solid samples were pre-
pared by means of the coning and quartering method.
The chemical composition of the precipitates was determined
using X-ray fluorescence spectrometry (XRF). X-ray diffraction
(XRD) was used to identify phases formed and to obtain an indica-
tion of the degree of amorphousness of some of the precipitates
produced. The samples were prepared for analysis using a back
loading preparation method. A PANalytical Empyrean diffractome-
ter with PIXcel detector and Fe filtered Co Ka radiation was used to
perform the analyses. X’Pert Highscore Plus software was used for
identification of phases, and phase quantification was done using
the Rietveld method. Amorphous phases were not taken into
account in the quantification.
A ZEISS EVO MA 15 Variable Pressure scanning electron micro-
scopy (SEM) with an energy dispersive X-ray spectrometer (EDS)
was used for analysis of particle characteristics, identification of
possible reaction products, and evaluation of nickel and copper
distribution in the precipitate. Particle size distribution of the pre-
cipitate was determined using a Saturn DigiSizer 5200 instrument.
Settling tests were performed to characterise the settling beha-
viour of precipitates produced with the different processes and at
different operating conditions. Suspensions of precipitate in water
were placed in a 1 L glass cylinder, mixed to obtain a homogenous
suspensions, and then placed on a flat surface. The settling of par-
ticles was captured using a video camera and the change in the
solid-liquid interface with time was calculated using a MatlabTM
interface tracking tool.
3. Results and discussion
3.1. Iron phosphate precipitation
3.1.1. Effect of pH and temperature
Fig. 1 shows results of seeded precipitation experiments con-
ducted at varying pH and temperature conditions. Iron was almost
completely precipitated out of solution after 20 min of reaction
time at all pH values (1, 2 and 3) and temperatures investigated
(40 °C, 60 °C and 80 °C). However, nickel and copper losses varied
with varying pH and temperature.
Copper losses can be ascribed to a combination of copper occlu-
sion and copper precipitation. At pH 3, in particular, no conclusions
regarding the contribution of occlusion to overall copper losses can
be made given the significant extent of copper precipitation
expected at this pH. It was not possible to identify the copper com-
pounds present in the precipitate during this investigation due to
the low copper and high iron content of the precipitate. However,
atacamite (CuCl23Cu(OH)2) has been reported to generally form as
the dominant copper precipitate during precipitation from chloride
solutions (Lundström et al., 2012; McDonald and Muir, 2007;
Valkama et al., 2014). In the case of nickel, losses are believed to
have occurred primarily because of occlusion since no potential
nickel containing solid phases are thermodynamically stable in
the range of operating conditions investigated in this study.
 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21 17

100% 40% 100% 40%

Ni, Cu precipitation

Ni, Cu precipitation
Fe precipitation

Fe precipitation
75% 30% 75% 30%

50% 20% 50% 20%

25% 10% 25% 10%

0% 0% 0% 0%
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)
Fe removal (%) Ni loss (%) Fe removal (%) Ni loss (%)
Cu loss (%) Cu loss (%)
(a) (b)
100% 100%

Fe, Ni, Cu precipitation

Fe, Ni, Cu precipitation

75% 75%

50% 50%

25% 25%

0% 0%
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

Fe removal (%) Ni loss (%) Fe removal (%) Ni loss (%)

Cu loss (%) Cu loss (%)

(c) (d)
Fig. 1. Seeded precipitation of iron phosphate depicting losses of nickel and copper at varying pH and temperatures: (a) pH 1, 40 °C, (b) pH 1, 60 °C, (c) pH 2, 40 °C, (d) pH 3,
40 °C.

It can be seen from Fig. 1(a) that during the first 10 min, the showed that the nickel and copper content of the precipitate
losses of nickel and copper increased with time and after that increased from 0.2% at pH 1 to 0.7% and 1.1%, respectively, at pH
nickel and copper losses appeared to start reducing and attained 3 and 40 °C. The significant increase in especially copper losses
equilibrium after about 30 min. It is proposed that this was due with an increase in pH was also due to the fact that the loss of cop-
to Ostwald ripening. It is suggested that nickel and copper losses, per through precipitation as species such as atacamite became
during the first 10 min, were due to occlusion of nickel and copper more significant compared to losses through occlusion. The precip-
liquid within the iron phosphate structure. As the smaller crystals itation of copper species made a larger contribution to the overall
of iron phosphate re-dissolved to form larger crystals, the trapped copper loss at the higher pH values, which could also explain why
liquid was released back into solution. Copper precipitation was the local maximum in metal losses at 10 min was less evident for
unlikely at pH 1 since formation of copper precipitates such as ata- the tests performed at the higher pH values.
camite have been reported to be significant only at pH values of Even though increasing the temperature from 40 °C to 60 °C and
approximately 2.6 and above (Lundström et al., 2012; McDonald 80 °C did not have as large an impact as increasing the pH, it can be
and Muir, 2007; Valkama et al., 2014). seen from Fig. 1(a) and (b) that lower temperature precipitation
The purity of these precipitates can thus be improved by lower- resulted in lower losses of nickel and copper for the same pH
ing supersaturation; low supersaturation ensures heterogeneous and retention time. In this study, the increase in nickel and copper
nucleation and subsequently well-defined crystal growth as well co-precipitation with an increase in temperature can be ascribed to
as the formation of larger particles, which limit co-precipitation the formation of iron compounds such as goethite or jarosite in
by occlusion. pH and temperature are process variables typically addition to the iron phosphate precipitate at the higher tempera-
recommended for supersaturation control in iron precipitation tures. This was confirmed by XRF analysis, which indicated that
applications (Claassen and Sandenbergh, 2007; Demopoulos, the iron to phosphorous molar ratio in the precipitate increased
2009; Dirksen and Ring, 1991). In general, lower supersaturation from 1.06 at pH 1 and 40 °C to 1.33 at pH 1 and 80 °C.
can be attained by decreasing the pH and increasing the
temperature. 3.1.2. Effect of seeding
The decreasing nickel and copper co-precipitation with a As was the case for iron precipitation in seeded tests (Fig. 1),
decrease in pH is evident from Fig. 1. At pH 1 and 40 °C, the nickel iron precipitation attained equilibrium with virtually complete
loss was 0.5% for a reaction time of 30 min. At this pH, temperature iron removal after 20 min when no iron phosphate seeding
and reaction time, the copper loss was 2.8%. Increasing the pH to 2 was employed. Seeding did, however, have an effect on the
resulted in nickel and copper losses of 14% and 77%, respectively, co-precipitation behaviour of nickel and copper, as shown in Fig. 2.
for the same reaction time and temperature. The nickel and copper Hove et al. (2009) reported that seeding favours formation of
losses were even higher for tests conducted at pH 3, regardless of larger, more pure and more stable particles at the expense of the
the temperature and reaction time. XRF analysis furthermore smaller, impure particles typical of homogeneous nucleation. In
18 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21
30%
Ni precipitation
20%
10%
0%
0 20 40
Time (min)
Unseeded
(a)
Fig. 2. Co-precipitation of (a) nickel and (b) copper during seeded and unseeded iron phosphate precipitation at 40 °C and pH 1.
the absence of seeding, homogenous nucleation results in high
nucleation rates and the rapid formation of a large number of small
particles, with growth typically being diffusion limited. Seeded
precipitation provides nucleation sites that allow well defined par-
ticle growth governed by the surface reaction rather than diffusion.
As a result, the possibility of nickel and copper occlusion is reduced
by the addition of seeding material, which explains the data shown
in Fig. 2. The dissolution of smaller and impure precipitates is fur-
thermore enhanced in seeded precipitation compared to unseeded
precipitation.
3.1.3. Precipitate characterisation
Scanning electron microscopy indicated that the precipitate
consisted of an amorphous iron phosphate precipitate with flakes
of sodium chloride. The iron phosphate precipitate consisted
primarily of spherical particles with a dense morphology. This
observation agrees with the results reported by Cruz et al. (1980)
and Garole et al. (2012), who ascribed the low co-precipitation of
other metallic cations to this specific precipitate morphology.
The colour of the precipitates formed in seeded and unseeded
experiments at all pH values at 40 °C was bright yellow, which is
characteristic of iron phosphate. At 60 °C, the precipitates formed
were still yellow but not as bright as the precipitates produced
at 40 °C. As the temperature was increased to 80 °C, the precipi-
tates were mostly light brown, especially in the case of unseeded
runs and runs conducted at pH 2 and pH 3. These observations
indicate that iron phosphate was formed in both seeded and
unseeded runs. The iron phosphate content of the precipitates
decreased with an increase in the temperature and pH as iron com-
pounds other than iron phosphate as well as copper precipitates
started to form.
SEM EDS results confirmed that the iron precipitation was pri-
marily due to iron phosphate formation given the clear similarity
between the distribution of iron and the distribution of phospho-
rous in the precipitate. XRF analysis also indicated an iron to phos-
phorous molar ratio of between 0.94 and 1.34; the values
significantly above the stoichiometric iron to phosphorous molar
ratio of 1 were observed for precipitates formed at higher temper-
atures and pH values, where precipitation of iron oxides con-
tributed to the overall iron removal (as discussed in Section 3.1.1).
In terms of XRD analysis, the iron phosphate precipitates pro-
duced at all conditions tested were found to be largely amorphous.
Apart from trace amounts of iron oxides detected in the precipi-
tates formed at higher temperature and pH conditions and trace
amounts of sodium chloride, no other crystalline phases were iden-
tified. Beck et al. (2011) reported similar observations, namely that
amorphous iron phosphate precipitated from the reaction of ferric
30%
Cu precipitation
20%
10%
0%
60 0 20 40 60
Time (min)
Seeded Unseeded Seeded
(b)
iron and sodium phosphate unless deliberate additional processes
were involved (Beck et al., 2011).
3.2. Hematite precipitation
3.2.1. Effect of pH and temperature
The effects of pH variations on the precipitation of hematite and
the resulting nickel and copper losses were similar to those
observed during the precipitation of iron phosphate. From Fig. 3
(a)–(d), it can be shown that iron precipitation was almost com-
plete (above 99% removal) after 20 min at pH values of 1, 2 and
3. Nickel and copper losses generally increased with an increase
in pH.
From Fig. 3(a) and (b), it can be seen that precipitation at 80 °C
recorded a similar iron removal profile to that observed at 60 °C.
Attempts to precipitate hematite at temperatures lower than
80 °C at pH 1 did, however, result in higher nickel and copper
losses; the nickel and copper losses observed at 30 min increased
from 3.5% and 1.7% to 13.2% and 11.9%, respectively, when the tem-
perature was decreased to 60 °C. Similar observations were made
for tests performed at pH 2.
As was the case for iron phosphate precipitation, combined pre-
cipitation of iron and copper occurred at the higher pH values, and
no conclusions regarding the contribution of occlusion to overall
copper losses can be made. At pH 1, the losses of nickel and copper
were attributed primarily to occlusion of liquid nickel and copper
within the akaganeite structure. Hematite is traditionally precipi-
tated at temperatures above 100 °C. Reducing the temperature
favours the precipitation of akaganeite, as shown by the results
presented in Section 3.2.3. Akaganeite is characterised by square
molecular channels formed through the connection of 4 by 2 rows
of octahedral structures. These channels in the akaganeite struc-
ture are sufficiently large to permit the passage of anions and other
impurities. Hematite, on the other hand, exhibits a compact crystal
structure. Akaganeite therefore exhibits a larger possibility of trap-
ping nickel and copper in its crystal lattice compared to hematite,
which explains why larger nickel and copper losses were observed
for the lower temperature precipitation tests.
3.2.2. Effect of seeding
Iron removal was rapid, with concentration profiles similar to
those shown in Fig. 3, in unseeded experiments. As was the case
with the iron phosphate precipitation process, seeding did result
in reduced nickel and copper losses, as shown in Fig. 4.
Dutrizac and Riveros (1999) demonstrated that hematite can be
precipitated at temperatures as low as 60 °C when precipitation is
seeded. It was however reported that even in seeded experiments,
akaganeite precipitation was not entirely avoided but seeding
 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21 19

100% 40% 100% 40%

Ni, Cu precipitation

Ni, Cu precipitation
Fe precipitation

Fe precipitation
75% 30% 75% 30%

50% 20% 50% 20%

25% 10% 25% 10%

0% 0% 0% 0%
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)
Fe removal (%) Ni loss (%) Fe removal (%) Ni loss (%)
Cu loss (%) Cu loss (%)
(a) (b)
100% 40% 100% 40%

Ni, Cu precipitation

Ni, Cu precipitation
Fe precipitation

Fe precipitation
75% 30% 75% 30%

50% 20% 50% 20%

25% 10% 25% 10%

0% 0% 0% 0%
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)
Fe removal (%) Ni loss (%) Fe removal (%) Ni loss (%)
Cu loss (%) Cu loss (%)
(c) (d)
Fig. 3. Seeded precipitation of hematite and loss of nickel and copper at varying pH and temperatures: (a) pH 1, 80 °C, (b) pH 1, 60 °C, (c) pH 2, 80 °C, (d) pH 3, 80 °C.

40% 40%
Ni precipitation

Cu precipitation

30% 30%

20% 20%

10% 10%

0% 0%
0 20 40 60 0 20 40 60
Time (min) Time (min)
Unseeded Seeded Unseeded Seeded
(a) (b)
Fig. 4. Co-precipitation of (a) nickel and (b) copper during seeded and unseeded hematite precipitation at 80 °C and pH 1.

accelerated its transformation to hematite. It is proposed that the The colour of precipitates produced in hematite runs depended
lower nickel and copper losses in seeded precipitation compared mostly on seeding. All unseeded experiments produced precipi-
to unseeded precipitation is attributed to the formation of tates with various shades of brown. The seeded experiments pro-
hematite in seeded precipitation as opposed to the formation of duced red precipitates, with the precipitate formed at pH 1 and
akaganeite in unseeded experiments. 80 °C having the deepest red colour characteristic of hematite. As
the pH was increased and the temperature decreased, the red col-
3.2.3. Precipitate characterisation our of the precipitates softened and, hence, the hematite content of
Scanning electron microscope images of the hematite precipi- the precipitate decreased.
tate indicated that the morphology of the particles were compact These observations were confirmed by the XRD data presented
with a number of agglomerates and aggregates. Elemental maps in Table 2, which illustrate the effect of temperature and pH on the
obtained using SEM EDS indicated a uniform distribution of nickel composition of the crystalline portion of the precipitate formed
and copper in the precipitate, which is similar to what was found during seeded hematite precipitation. The ratio of crystalline
for iron phosphate precipitation. precipitate to amorphous precipitate (e.g., ferrihydrite) was not
20 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21

Table 2 140
Mineralogical composition of crystalline precipitates formed at different conditions of
seeded hematite precipitation. 120

Filtration rate (mL/min)

Conditions Hematite Akaganeite Other 100
pH 1, 60 °C 63 37 –
pH 1, 80 °C 96 – 2% magnetite, 2% halite
80
pH 2, 80 °C 59 41 –
60
pH 3, 80 °C 56 44 –
40
quantified. The percentage hematite in the crystalline precipitate 20
increased with a temperature increase from 60 °C to 80 °C as well
as with a decrease in pH. These results are in agreement with the 0
pH 1 pH 2 pH 3
explanation regarding increased nickel and copper losses at high
pH and low temperature conditions, which was ascribed to the 60°C 80°C 90°C
formation of increasing amounts of akaganeite and decreasing
Fig. 6. Hematite filtration rates as a function of pH at various temperatures.
amounts of hematite. Although copper precipitates such as ata-
camite were not detected using XRD analysis, this was likely due
to initial solution composition which resulted in a very small 3.3.2. Sedimentation
amount of copper precipitate forming compared to the amount Analysing the settling profile of seeded iron phosphate precipi-
of iron precipitate formation. tated at pH 1 and 40 °C indicated that iron phosphate precipitate
settled completely after approximately 26 min, forming a clear
3.3. Solid-liquid separation solid-liquid interface. The clarity of the settling interface reduced
with an increase in pH, and settling required approximately
3.3.1. Filtration 36 min to be completed for the precipitate formed at pH 2 and
From Fig. 5, it can be seen that iron phosphate precipitates pro- 40 °C. The solids produced during hematite precipitation
duced at all conditions tested were filterable with filtration rates experiments could not be settled by gravity, with no solid-liquid
between 50 mL/min and 130 mL/min; these rates are around the interface forming.
average filtration rate of 83 mL/min reported by Cohen et al.
(2005). The effect of temperature and pH on filtration rates can 3.4. Process comparison
be explained in terms of the particle size distribution of the precip-
itate. As was discussed in Section 3.1.1, decreasing the pH and Based on the experimental results obtained, a comparison of the
increasing temperature resulted in lower supersaturation; this key operating conditions and performance criteria between iron
enhanced heterogeneous nucleation, formation of larger particles, phosphate precipitation and hematite precipitate is summarised
higher filter cake porosity, and hence better filterability. in Table 3.
It was practically impossible to filter precipitates produced dur- All iron removal and nickel and copper losses are reported for
ing hematite precipitation performed without seeding. Seeded the samples taken at 30 min, since this was typically the time
hematite precipitation experiments were, however, easily filtered. required for the iron precipitation to reach equilibrium and at
As illustrated in Fig. 6, the filtration rate was in the ranges which point the nickel and copper losses were close to a minimum.
35–55 mL/min at pH 1, 65–105 mL/min at pH 2 and 110–130 mL/ Given the high nickel and copper losses at pH values above pH 1,
min at pH 3. Cohen et al. (2005) attributed better filterability of the fact that iron removal in excess of 98% was achieved at pH 1,
precipitate produced in seeded experiments to the formation of and the acidity of typical pregnant leach solutions, iron removal
hematite in seeded precipitation as opposed to akaganeite being by seeded precipitation would not be performed at pH values
the main precipitate formed in unseeded precipitation. The
increase in filtration rate with an increasing pH can be attributed
to the formation of aggregates and agglomerates, which was more Table 3
significant for the hematite process than for the iron phosphate Summarised comparison of key parameters for seeded iron phosphate and seeded
hematite precipitation processes.
precipitation process due to smaller particles formed in the hema-
tite process. The formation of aggregates and agglomerates is Parameter Iron phosphate Hematite
enhanced by reducing the zeta potential, which decreases with Seeding Unseeded precipitation Unseeded precipitation
increase in solution pH. resulted in increased resulted in increased nickel
nickel and copper losses as well as
140 and copper losses poor filtration
Reagents Neutralizing reagent Neutralizing reagent
Filtration rate (mL/min)

120 (NaOH) and PO3 3

4 . PO4 (NaOH)
can be regenerated
100 Iron removal 98.8% (40 °C)
at pH 1 99.9% (60 °C) 98.2% (60 °C)
80 99.8% (80 °C) 99.6% (80 °C)
Nickel losses 0.5% (40 °C)
60
at pH 1 9.2% (60 °C) 13.2% (60 °C)
40 8.7% (80 °C) 3.5% (80 °C)
Copper losses 2.8% (40 °C)
20 at pH 1 33.1% (60 °C) 11.9% (60 °C)
20.8% (80 °C) 1.7% (80 °C)
0 Filtration 50–130 mL/min 35–130 mL/min
pH 1 pH 2 pH 3 Sedimentation Settling complete after No settling observed
26 min
40°C 60°C 80°C Precipitate Bright yellow, easy to Deep red, difficulty to clean
colour clean
Fig. 5. Iron phosphate filtration rates as a function of pH at various temperatures.
 S. Masambi et al. / Minerals Engineering 98 (2016) 14–21
above pH 1. The most suitable precipitation process for a specific
application will depend on a number of factors such as the operat-
ing temperature of the upstream and downstream unit operations,
main operational objectives, and operating costs in specific local
markets.
At 40 °C, the iron phosphate precipitation process can remove
98.8% of iron in solution with minimal nickel and copper losses
(0.5% and 2.8%, respectively) after 30 min. The iron removal
increased to 99.9% when the temperature was increased to 60 °C,
but the nickel and copper losses increased to 9.2% and 33.1%,
respectively. At the same temperature, the hematite precipitation
process achieved 98.2% iron removal with higher nickel losses
(13.2%) but significantly lower copper losses (11.9%) than the iron
phosphate precipitation process. At 80 °C, the hematite and iron
phosphate precipitation processes achieve comparable iron
removal (99.6% and 99.8%, respectively). Based on the nickel and
copper losses, however, it is clear that the hematite precipitation
process would be the preferred option at the higher temperature.
4. Conclusion
Iron phosphate precipitation performed at a temperature of
40 °C and pH 1 achieved 98.8% iron removal after 30 min reaction
time with 0.5% nickel and 2.8% copper losses through
co-precipitation. Although iron precipitation increased with an
increase in temperature, the nickel and copper losses also
increased to 8.7% and 20.8%, respectively, at 80 °C. These high
nickel and copper losses render the iron phosphate precipitation
process less desirable compared to the hematite process at higher
operation temperatures.
The performance of the hematite precipitation processes gener-
ally improved with an increase in temperature. At 80 °C and pH 1,
99.6% iron removal with 3.5% nickel and 1.7% copper losses were
achieved after 30 min. For both processes, the nickel and copper
losses increased significantly when the pH was increased or when
seeding was not used.
The precipitate formed during both the seeded iron phosphate
precipitation and the seeded hematite precipitation was easily fil-
terable. The solids produced in the iron phosphate precipitate pro-
cess showed good settling behaviour, with settling tests yielding a
clear solid–liquid interface after 26 min of gravity settling; in the
case of hematite precipitate, no settling was however observed
after 8 h.
The iron phosphate precipitation process has been shown to be
a suitable iron removal process for consideration in certain appli-
cations, for example where the upstream or downstream unit
operations are operated at lower temperatures than what would
typically be required for efficient seeded hematite precipitation.
21
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