Minerals Engineering 18 (2005) 1344–1347

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Technical note

Precipitation of iron from concentrated chloride solutions:

Literature observations, challenges and preliminary
experimental results
a,*
B. Cohen , D.S. Shipley a, A.R. Tong b, S.J.G. Casaroli a, J.G. Petrie a

a
Department of Chemical Engineering, University of Sydney, NSW 2006, Australia
b
Intec Ltd., Gordon Chiu Building, University of Sydney, NSW 2006, Australia

Received 15 May 2005; accepted 24 July 2005

Available online 16 September 2005

Abstract

The removal of iron is necessary during the purification of leachates from zinc bearing ores prior to electrowinning due to its
negative impact on both product quality and current efficiency. Whilst precipitation down to acceptable levels is readily achieved,
the challenge lies in producing an easily filterable precipitate which is relatively pure (for resale and/or reuse). Crystalline hematite is
an iron precipitate which potentially fulfils these requirements. Some work has been presented in literature on precipitation of hema-
tite from sulphate solutions and dilute chloride solutions, however no work has been found on the selective precipitation of hematite
from concentrated halide solutions. This technical note presents some preliminary observations on the selective formation of hema-
tite from a leachate which originated from the zinc recovery process developed by Intec Ltd. The process is novel in the use of a
mixed halide leachant over the traditional sulphide leachant, with the advantages of operation at low temperatures and atmospheric
pressure, and that the leachant may be regenerated and recycled. The solution contains relatively high chloride/bromide concentra-
tions which makes direct extrapolation from literature reports difficult.

2005 Elsevier Ltd. All rights reserved.

Keywords: Hydrometallurgy; Precipitation; Filtration

1. Introduction and requires lower temperatures (80 C) compared

The Intec zinc recovery process uses a mixed chlo-
ride/bromide solution to leach zinc from concentrates
from zinc sulphide ores. The process has a number of
environmental and cost benefits over traditional pro-
cesses. Firstly, the BrCl

2 oxidant used for leaching elim-
inates the need for roasting of the concentrate prior to
leaching as is required in conventional RLE processes.
Secondly, the leach is operated at atmospheric pressure,
*
Corresponding author. Tel.: +61 02 9351 7132; fax: +61 02 9351
2854.
E-mail address: bcohen@chem.eng.usyd.edu.au (B. Cohen).
with other processes. Thirdly, recycling the leachant re-
sults in a lower waste management cost and environ-
mental impact. Finally, secondary and precious metals
may potentially be selectively recovered in a saleable
form, further increasing profitability and reducing waste
management costs.
The process consists of three circuits, being leaching,
leachate purification and electrowinning. Leaching is
conducted using a solution containing the BrCl
2 anion,
which is regenerated in the electrowinning step and has
an oxidising potential of 1000 mV (SHE). The leachate
obtained has a nominal zinc concentration of 65 g/l,
an iron concentration to the order of 15 g/l, and Cu,
Cd, Pb, Mn and Mg, with concentrations of all species

0892-6875/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.07.013
 B. Cohen et al. / Minerals Engineering 18 (2005) 1344–1347
depending on the original ore composition. High salt
concentrations are also present from the leaching
solution.
Leachate purification includes precipitation and
cementation for metals removal prior to electrowinning.
Iron precipitation, the subject of this note, represents a
significant challenge. In this note the issues associated
with iron removal from solution are identified, some
of the literature findings relating to the precipitation in
chloride media are presented and preliminary experi-
mental observations on iron removal from the Intec
leach solutions are discussed.
2. Literature findings
Iron is theoretically easily precipitated from solution
as oxides, hydroxides and other complexes. Various pro-
cesses have been used for this purpose, including those
which aim to form jarosite, goethite and hematite. The
type of precipitate and process conditions under which
it was formed will determine the filterability, stability
and potential for reuse/disposal requirements of the fi-
nal product.
The jarosite process is the most commonly used
process in sulphate environments. Jarosite is a complex
basic iron sulphate of the form 2MFe3(SO4)2(OH)6,
where M represents one of the ions Na+, NHþ +
4 , H 3O ,
+ + 2+
Li , K , 1/2Pb . The process has the disadvan-
tages of co-precipitation of other metal species such
as Pb and Ag with the product, potentially resulting
in the need for disposal in hazardous landfill and lim-
ited potential for reuse, and significant solid volumes
which require disposal (Cornell and Schwertmann,
1996).
The goethite process removes iron from an aqueous
solution as filterable goethite (FeO Æ OH) (Ismael and
Carvalho, 2003). Goethite is formed as either a-goethite
or b-goethite (akaganeite), with the former being more
crystalline and easily filterable than the latter. The pro-
cess is also widely used in industry, but also gives rise to
significant volumes of precipitate.
Hematite (a-Fe2O3) is a preferred route for iron re-
moval due its stability, density and relatively purity, as
well as high levels of iron, suggesting relatively easy dis-
posal or potential for resale (Riveros and Dutrizac,
1997). Potential markets include cement production,
the iron industry and the manufacture of pigments (Is-
mael and Carvalho, 2003). The formation of hematite
is being pursued in the Intec process.
Some work has been presented in literature on forma-
tion of hematite at high pressures. Limited work has
been found with respect to formation of iron in chloride
media, particularly in complex environments, and at low
temperatures and under atmospheric pressure. Low tem-
peratures and pressures are desirable for the precipita-
1345
tion step in the Intec process due to the fact that the
leach is conducted at 80 C and 1 atm. Precipitation at
conditions close to these would remove the costs associ-
ated with heating and pressurising in order to achieve
hematite precipitation.
Perhaps the most significant work in the formation of
hematite in chloride media is that of Riveros and Dutri-
zac (1997) and Dutrizac and Riveros (1999). In their
work a combination of three key variables was found
to be responsible for influencing hematite formation.
These variables were temperature, reaction time and
amount of hematite seeding. Other particular observa-
tions by these authors were:
• In the absence of hematite seeding, pure hematite is
formed at temperatures of >135 C after a reaction
time of up to 16 h. At temperatures of between 100
and 125 C after a 96 h reaction, a mixture of hema-
tite and akaganeite is found. Below 125 C only akag-
aneite is formed for precipitation periods of up to
16 h. The proposed mechanism for hematite forma-
tion in the absence of seed is by redissolution and pre-
cipitation of akaganeite (b-FeO Æ OH) which is
formed in the early stages of the experiment. The lat-
ter reaction was explored at pH 5–6.
• The addition of a hematite seed allows for precipita-
tion of hematite in relatively short reaction times
(<3 h), at temperatures as low as 60 C. The mecha-
nism for this formation is proposed to be direct
precipitation.
Whilst these results represent a significant starting
point for exploring the potential for hematite pre-
cipitation in the Intec process, the need exists for
experimental work whether these results are directly
applicable. In particular the following key differences
between the current work and that presented in litera-
ture are identified:
• The Intec process has significantly higher chloride
concentrations (to the order of 1.2 M from Dutrizac
and Riveros (1999) vs 8 M in the current work),
and chlorine has been identified to promote the ini-
tial formation of akaganeite (Knight and Sylva,
1974). It is unknown whether higher chloride concen-
trations would inhibit the subsequent conversion to
hematite.
• The Intec leachate solution contains a variety of other
cation and anion species, which present the potential
for a number of complex interactions and which may
thus change the precipitate formed.
• In the Intec precipitation process, it is desirable to
achieve iron precipitation at a relatively low pH to
limit co-precipitation of other metal species. Other
work has concentrated on precipitation at higher
pHs.
1346 B. Cohen et al. / Minerals Engineering 18 (2005) 1344–1347
3. Experimental aims and procedure
The aim of the work of which preliminary observa-
tions are presented in this paper, is to determine the
applicability of literature findings to the Intec leachate
solutions, in particular to:
• Determine the temperature and reaction times
required for hematite formation.
• Identify and optimise the experimental variables (pH,
seeding, reaction time and temperature) which affect
filtration of the product, and determine whether
improved filterability is linked to hematite formation;
and
• Assess the purity of the precipitates formed to assess
their suitability for reuse or sale.
A synthetic leach liquor was made to reflect metal
concentrations expected in practice. The liquor was
heated to the desired reaction temperature and the
pH raised from 0 to the reaction pH by gradually
adding a slurry of calcium carbonate (CaCO3). The
pH was monitored throughout the experiment and
where necessary additional CaCO3 was added to raise
the pH. Filtration was conducted in a constant
pressure filter. Solids were analysed for metals con-
tent via digestion followed by Varian ICP-AES, as
well as for the iron phases using XRD. Liquid
samples were also analysed for metals content via
ICP-AES.
4. Preliminary findings
4.1. Extent of iron removal from solution and product
purity
As expected, significant removal of iron is possible
both with and without seeding, with the remaining
iron in solution decreasing as both the amount of
seeding and pH is increased. After 4 h (at 70 C)
and with 10 g/l of seeding at a pH of 0.9 less than
10% of the iron remains in solution. This drops to
3% with 20 g/l seeding. At a pH of 1.5 and 2.0 at
70 C (with or without seeding), no iron remains in
solution.
One of the aims of the process is to recover a product
which is potentially saleable, and as such it is desirable
to limit the co-precipitation of other metals. At all
conditions tested, the proportion of other metals re-
moved from solution is consistently less than 1% of
the final solid mass. This is as expected due to the low
pH range considered in this work. The importance of
these metals will depend on the ultimate fate of the iron
precipitates.
4.2. Impact of process variables on filterability of
precipitates
• pH: The impact of pH on filterability was tested for
two levels of hematite seeding (10 g/l and 20 g/l,
selected as spanning the range of those found in liter-
ature to be effective in promoting hematite forma-
tion). Little impact of precipitation pH or level of
seeding on filterability was shown for precipitation
times of 4 h. On this basis, a constant pH of 0.9
was used for all further tests to limit co-precipitation
of other metals.
• Temperature: Temperature appeared to have a signif-
icant impact of the filtration kinetics. Initial testing
was performed at 70 C, where filtration was virtually
impossible at 4, 24 and 72 h reaction times. However
when the temperature was increased to 100 C and
110 C, filtration was observed to be possible, with fil-
tration of a 500 ml sample taking 10–40 min depend-
ing on the level of seeding. The improved filtration
was attributed to the formation of hematite at higher
temperatures.
• Seeding: Seeding with hematite results in a significant
increase in the rate of filtration over all investigated
temperatures (70 C, 100 C and 110 C) and reaction
times (4 h and 24 h). For example at 100 C (24 h) the
unseeded filtration time was approximately 430 min/
l, however when 10 g/l seeding was introduced the fil-
tration proceeded at approximately 12 min/l. Increas-
ing the level of seeding from 10 g/l to 20 g/l does
not make a significant difference to the filtration
profiles.
• Reaction time: A significant improvement in filter-
ability is shown between 24 and 72 h in unseeded
experiments run at 100 C. It is suggested that the
improved filterability can be linked to the conversion
of akaganeite to hematite in the longer experiments as
discussed below.
4.3. XRD results
XRD results showed that, for temperatures up to
90 C in the absence of seeding, the precipitated iron
mineral was akaganeite, even after precipitation periods
of 120 h. However, when the temperature was raised to
100 C, the initial akaganeite product formed after 4 h is
converted into a mixture of akaganeite and hematite
after 72 h. When the temperature was raised to 110 C,
hematite was the major iron mineral formed.
These results support the literature suggestion that
precipitation of hematite is preceded by akaganeite for-
mation, which then converts to more thermodynami-
cally stable hematite by a dissolution/precipitation
mechanism. A Reitveld refinement (Rietveld, 1969) sug-
gested that the product contained to the order of
 B. Cohen et al. / Minerals Engineering 18 (2005) 1344–1347
71 wt.% hematite, 5 wt.% akaganeite, and 24 wt.% anhy-
drite. This suggests that the conversion to hematite was
almost complete after 72 h. Further work is required to
determine the actual rate of conversion.
5. Summary and future work
This technical note has presented some preliminary
observations with respect to work that is being done
to explore the selective precipitation of iron as hematite
from a complex solution from zinc leaching. In sum-
mary, the work has demonstrated the following:
• Removal of iron from solution down to acceptable
levels for further processing is possible with and with-
out seeding.
• Filterability is significantly improved as both temper-
ature and reaction time is increased.
• Seeding significantly improves the filterability of
precipitates.
• Hematite formation in the absence of seeding is pos-
sible at temperatures of 110 C, given a precipitation
time to the order of 72 h.
• Formation of hematite was suggested to be via slow
dissolution of akaganeite and subsequent re precipi-
tation of hematite.
Further work is being conducted to determine the
optimal conditions for iron removal to give the desirable
properties of a hematite product with improved
filterability.
1347
One of the challenges is to resolve the trade-off be-
tween long residence times required for formation of
hematite at lower temperatures, energy requirements
for hematite formation at higher temperatures in shorter
time periods and the potential for reuse of the product.
This trade-off will be a key focus of the design stage of
this process.
Acknowledgments
This work was funded by a Linkage grant from the
Australian Research Council in conjunction with Intec
Ltd. Intec Ltd. also contributed human and physical re-
sources to this project.
References
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