Minerals Engineering 16 (2003) 3139

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Iron recovery from sulphate leach liquors

in zinc hydrometallurgy
M.R.C. Ismael, J.M.R. Carvalho

Dep. Eng. Qu
mica, Instituto Superior T

ecnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Received 25 June 2002; accepted 30 October 2002

Abstract
Iron is usually present in leach solutions and its elimination is a major operational problem in zinc hydrometallurgy. The recovery of iron from such solutions is usually carried out by precipitation as jarosite, goethite or hematite. These residues, contaminated with heavy metals ions such as Zn, Pb, In, Ga, Ge, Co and sulphur, are environmentally unacceptable and their disposal
in controlled ponds is very expensive. This fact justies the interest in producing iron as a marketable productpure hematite. With
this purpose solvent extraction is being investigated as a promising alternative for the recovery of iron from leach solutions.
2003 Elsevier Science Ltd. All rights reserved.
Keywords: Hydrometallurgy and solvent extraction

1. Introduction
Iron is present as an undesirable constituent of zinc
ores, concentrates and calcine oxides. The leaching of
concentrates results in the solubilisation of the desired
metal together with some iron. Iron constitutes a severe
impurity in zinc solution and must be removed before
electrolysis.
Nowadays iron is usually removed from leaching
solutions by precipitation (Dutrizac, 1980) as goethite
(Boxal and James, 1986; Torfs and Vliegen, 1996) or
hematite (Ropenack, 1986; Onazaki and Kuramochi,
1986) but in most existing electrolytic zinc plants, the
method for iron removal involves its precipitation as
jarosite (Steintveit, 1971; Haigh and Wood, 1972; Arregi
et al., 1980; Scott et al., 1986; Tamargo et al., 1996;
Buban et al., 1999). However, this process has economical disadvantageous, due to the high cost of impounding jarosite in controlled tailing ponds. Otherwise,
the exposure of such residue, contaminated with heavy
metals such as Zn, Se, In, Ge and sulphur, to atmospheric conditions will cause environmental problems
(Berg and Borve, 1996; Garcia and Valdez, 1996; Welham et al., 2000).

Corresponding author. Tel.: +351-21-8417311; fax: +351-218499242.

E-mail address: pcjcarv@popsrv.ist.utl.pt (J.M.R. Carvalho).

In order to overcome these problems it is required to

remove iron from aqueous solutions as marketable iron
productsi.e. pure hematite that can be used as a pigment or as raw material in steel making industry. Pure
hematite can be obtained if iron is removed from
aqueous solutions by the solvent extraction technique
with selective extractants. Although dierent extractants
have been tested the solvent extraction has not yet
achieved success in the zinc hydrometallurgy. However,
the various approaches used so far are reviewed in this
paper.

2. Iron elimination by precipitation techniques

2.1. Jarosite process
The inclusion of the jarosite process in electrolytic
zinc plants allowed an improvement in the zinc recovery to a value as high as 9698%. This fact is related
with the possibility of recovering zinc in ferrite
(Fe2 O3
ZnO) besides zinc in ZnO. Obviously, this result the extensive study performed on the jarosite type
compounds.
2.1.1. Factors aecting the precipitation of iron as jarosite
Jarosites are a complex basic iron sulphate, and their
formation is represented by the following equilibrium:

0892-6875/03/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved.
PII: S 0 8 9 2 - 6 8 7 5 ( 0 2 ) 0 0 3 1 0 - 2

32

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

3Fe2 SO4 3 M2 SO4 12H2 O

$ 2MFe3 SO4 2 OH6 6H2 SO4

where M represents any of the ions Na , NH

4 , H3 O ,

1
2
Li , K , 2Pb .
According to Babcan (1971), who studied the hydrolysis of a solution containing ferric sulphate and
potassium hydroxide, the jarosite stability zone is within
pH 1 to 3 and at temperatures between 20 and 200 C.
At low pH no precipitate occurs, at a high pH mainly
goethite (up to 100 C) and hematite (above 100 C)
exist.
Special attention has also been paid to the jarosite
precipitation reaction, mostly in the context of zinc solutions (Dutrizac et al., 1980; Arregi et al., 1980; Almeida, 1988; Limpo et al., 1976). Dutrizac and Dinardo
(1983), Dutrizac (1983a, 1996, 1999), Dutrizac and
Jambor (1984a,b), has published extensive work concerning the most relevant parameters on jarosite
precipitation. The experimental results show that the
process is very dependent on temperature, pH and contact time. In fact, increasing the temperature from 70 to
110 C increases considerably the rate of precipitation. In
order to avoid high cost autoclave equipment a temperature of 97 C was selected and it was veried that iron is
readily precipitated in several hours. According to different authors (Kershaw and Pickering, 1980; Dutrizac
and Dinardo, 1983; Dutrizac, 1983a; Dutrizac and
Jambor, 1984a,b; Babcan, 1971; Teixeira and Tavares,
1986) the ideal conditions for jarosite formation are
temperature )95 to 100 C, pH )1.5 to 1.8, vigorous
agitation and the presence of seed material (jarosite).
The weakness of the precipitation process seems to be
the co-precipitation of various metals ions (Cu, Zn, Co,
Ni, Mn, In, Ga, Ge, Al) present in the solution. Dutrizac
(1983b, 1984) and Dutrizac and Chen (2000) observed
that divalent metals are not as incorporated in jarosite
as the trivalent ones. He has also veried that the coprecipitation increases with the pH of the solution, with
concentration of contaminants and decreases with the
iron concentration.
The exhaustive work carried out on jarosite precipitation was very important for the modications (Haigh
and Pickering, 1970; Haigh and Wood, 1972; Haigh and
Pammenter, 1981; Gordon and Pickering, 1975; Gordon, 1977; Steintveit, 1970; Pammenter et al., 1986;
Matthew et al., 1983) to the conventional jarosite process to be carried out.

2.1.2. Jarosite process at electrolytic zinc plants

The conventional jarosite process was developed and
patented simultaneously by the Asturiana de Zinc S.A.
of Spain, by The Electrolytic Zinc Co. of Australasia
and by Det Norske Zinkkompari A/S of Norway in the
early 1960s. Subsequently a large number of zinc pro-

ducers have implemented this process. In this process

iron is precipitated from the hot acid leaching solution
at elevated temperatures (9597 C) in the presence of
sodium or ammonium ions. The reaction of precipitation liberates acid, which must be neutralized with zinc
calcine. This one is only partially dissolved; the rest
stays with the jarosite precipitate. Consequently considerable amounts of zinc and valuable metals such as
lead, silver, indium, gallium, germanium, etc. are lost
(Dutrizac, 1980; Dutrizac and Dinardo, 1983; Dutrizac
and Jambor, 1984a,b) in addition to having contaminated residues which might lead to environmental problems.
In the mean time some modications were carried out
in the conventional jarosite process with the purpose of
a high zinc recovery and the production of a more pure
residue. One of these modications consists on carrying
out a pre-neutralization of the hot acid solution with zinc
calcine. The calcine which is not solubilized is recycled
to the hot acid leaching step while the leach solution at
pH 1.51.7 is sent to the jarosite precipitation stage.
Such pre-neutralization reduces (Steintveit, 1971) or
even eliminates (Haigh and Pammenter, 1981; Pammenter et al., 1986) the necessity of adding zinc calcine
in the precipitation stage. When jarosite contains some
calcine this can be partially removed washing the precipitate with a hot acid solution (Steintveit and Dyvik,
1972). The incorporation of pre-neutralization and
jarosite washing stages in the jarosite process leads to a
higher zinc recovery (9899%).
Stiges and Arregui (1972) proposed to carry out the
jarosite precipitation in two stages. The feed at the rst
stage of precipitation consists of hot acid leach liquor,
the residue of the second stage of precipitation (jarosite
contaminated) and calcine (neutralizing agent). The
acidity of this solution must remain high enough to
dissolve all calcine added. The jarosite obtained has a
low content of ferrite and is sent to disposal. The remaining solution, with high content of iron, is sent to
the second stage of precipitation. Here the precipitation
occurs at higher pH, adding calcine, which allows the
reduction in the concentration of iron in solution to
trace levels. This jarosite is contaminated with calcine
and is recycled to the rst tank while the remaining
solution is sent to electrolysis.
The modications above described and introduced by
zinc producers in theirs plants had only partial success.
In fact jarosite actually produced is more pure but is not
totally free of heavy metal and sulphate. This residue
has no applicability and it is landlled (Ek, 1986; Berg
and Borve, 1996; Buckle et al., 1996; Garcia and Valdez,
1996). The severe legislation concerning storage of
contaminated residues makes compulsory the use of
impermeable ponds and serious control of the pond
waters (Pophanken, 1996). All these facts lead as a real
hypothesis to produce marketable hematite instead of

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

jarosite. Some authors have already investigated the

possibility of converting jarosite into hematite with the
purpose of treating impounded jarosite (Dutrizac, 1990;
Geldart et al., 1996).
2.2. Goethite process
The goethite process is also successfully implemented
in the electrolytic zinc industry. The elimination of iron
from an aqueous solution as goethite (FeO
OH), implies that the concentration of ferric ion in solution must
not exceed 1 g/l. This can be accomplished by reducing
all ferric ions to the ferrous state (Vieille Montagne
technique; Boxal and James, 1986) or by adding the
concentrated ferric solution to the precipitation vessel at
the same rate of goethite precipitation (electrolytic zinc
plants; Davey and Scott, 1976). Slow precipitation leads
to the production of a well-crystallized precipitate
(a-FeO
OH) while higher rates of precipitation lead to
the formation of akagenite (b-FeO
OH; Davey and
Scott, 1975; Agatzini et al., 1986). The formation of the
latter is undesirable because ltration becomes more
dicult.
The goethite is precipitated by the reaction
Fe2 SO4 3 4H2 O $ 2FeO
OH 3H2 SO4
This reaction must be carried out at 8090 C and pH 2
3 (Posnjak and Merwin, 1922; Davey and Scott, 1976;
Agatzini et al., 1986) and it is necessary to neutralize the
acid formed during the goethite precipitation. Appreciable contamination of the precipitated with zinc ferrite
also results. Commonly the residue is washed in order to
reduce the level of impurities. However, this washing is
not ecient enough.
One advantage of precipitating iron as goethite instead of jarosite is the low volume of the waste goethite.
The Union Miniere (Torfs and Vliegen, 1996) says that
goethite oers some possibilities for further treatment
such as inertisation and solidication or smelting and
slag fuming. In both cases an inert material is obtained
that could be used in construction industry.
2.3. Hematite process
One marked feature of the removal iron from solutions as hematite is related to the possibility of using it in
the cement, in the iron industries and or as pigment.
This means that a major problem in the zinc industry i.e.
the accumulation of residues is overcome.
The hydrolysis of ferrous sulphate to hematite is
represented by the following reaction:
2FeSO4 1=2O2 2H2 O $ Fe2 O3 2H2 SO4
which takes place under an oxidizing atmosphere (pO2 >
5 bar) and at high temperatures (T > 185 C; Ropenack,
1982).

33

According to literature data at 200 C, iron is eliminated as hematite (Babcan, 1971; Tozawa, 1986; Umetsu
et al., 1977), as the reaction proceeds some acid is liberated into solution and when the acid concentration
rises to 65 g/l, FeOHSO4 is preferentially formed. Thus
dierent mixtures of Fe2 O3 /FeOHSO4 are obtained,
depending on the initial iron concentration. The decrease in temperature to 185 C decreases the maximum
acid concentration allowed for the hematite to precipitate down to 56 g/l.
The presence of zinc sulphate in solution displaces the
phase boundary between Fe2 O3 and FeOHSO4 to a
higher acid level and higher temperatures. For example
at 185 C hematite is stable up to 84 g/l of sulphuric
acid, if the solution contains 100 g/l of zinc sulphate
(Umetsu et al., 1977).
The requirement of this process to operate at high
temperatures is translated into high capital and operational costs. However, the problems related with the
storage of residues is minimized because the hematite
produced is sold to cement makers (Iijima Renery,
Japan, Onazaki and Kuramochi, 1986 and Ruhr, Zink,
Germany, Ropenack, 1986). In fact the hematite obtained has no quality to be used in the steel industry.
Pure hematite only can be produced if it is precipitated
from a pure iron solution. This one can be obtained
using the solvent extraction technique and a selective
extractant to remove iron from zinc liquors.

3. Iron removal by liquidliquid extraction

The implementation of solvent extraction process in
hydrometallurgical zinc plant has not yet achieved success although there has been considerable work carried
out on the use of dierent extractants. The various approaches that have been taken and the remaining
problems are reviewed below.
3.1. Organophosphorus acids
The extraction of iron with organophosphorus acids
has been extensively studied (Sato and Nakamura, 1971;
Ritcey and Ashbrook, 1984; Demopoulos et al., 1996;
Van Weert et al., 1998; Demopoulos and Principe, 1999;
Naik and Dhadke, 1999; Su
arez et al., 2002). Demopoulos and Pouskouleli (1989), Demopoulos et al.
(1993), Demopoulos and Principe (1998) selected among
them MEHPA(mono (2-ethylhexyl)phosphoric acid).
These authors veried that the latter extracted Fe3 at
high rates and very high loadings (up to 25 g/l for 25%
(v/v) MEHPA) from feed liquors of varying H2 SO4
concentrations (up to 150 g/l). They also veried that
iron is selectively extracted over zinc and copper; the
separation factors Fe/Zn and Fe/Cu are respectively
3000 and 1000. More recently CEZinc/CANMET/

34

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

McGill University (Demopoulos et al., 1996) carried out

continuous tests in a pilot plant using as aqueous phase
a solution of 50 g Fe l1 , 110 g Zn l1 , 50 g H2 SO4 l1
and as organic phase a partially loaded (14 g Fe l1 )
MEHPA (40% v/v)/tridecanol (20% v/v)/Varsol 140
(aliphatic diluent) mixture. After the extraction step,
and using an aqueous/organic ratio 2=1, the concentration of iron in the ranate decrease to 5 g/l. The
loaded organic phase was contacted with an HCl (8 N)
solution at A=O 2=1 to produce a strip liquor with 76
g Fe l1 . According to Demopoulos and Principe (1998)
the weaknesses of this process are the inadequate concentration of iron in stripping solution (<100 g Fe l1 )
to produce economically Fe2 O3 by pyrohydrolysis
(Karner, 1986; Poy, 1996; Peek et al., 1996) and the
transport of SO2
4 by the extractant most likely as part

of the extracted Fe3 species: FeHSO2

4 and/or FeSO4 .
2
The SO4 is a contaminant not allowed in the marketable Fe2 O3 product.
Thus far, DEHPA ((di-2-ethylhexyl) phosphoric acid)
is one of the most widely studied extractants to remove
iron from zinc solutions. Sato and Nakamura (1971),
Sato et al. (1985) and Demopoulos and Gefvert (1984)
show that distribution ratio (DFe ) of iron in DEHPA
decreases abruptly with the acidity of aqueous phase
(ex: DEHPA 0:05 M in kerosene DFe 3 when
H2 SO4;initial 0:1 M and DFe 0:06 for H2 SO4;initial 2
M). In 1983 Hoh and co-workers compared the extraction of iron into several diluents (toluene, xylene, n-octane and Kermac 470 (a mixture of parans,
naphtalenes and aromatics)) and noticed that the increase in the solvent polarity decreases the separation
factor of iron over zinc. The percentage of extraction of
iron and zinc with DEHPA (20% in Kermac 470) increases with pH and temperature, becoming constant in
a pH range of 12.2. In terms of the iron/zinc separation
the optimum is achieved at pH 1.5. Addition of TBP
(tributyl phosphate) to the above system enhanced the
iron extraction over zinc extraction (synergistic eect;
Hoh et al., 1983; Sahu and Das, 1997).
Vazarlis and Neou-Syngoyna (1984) leached a Creek
Copper concentrate with a sulphuric acid solution and
obtained a solution with 19.3 g/l copper, 8.2 g/l zinc and
2.7 iron g/l. The extraction/separation of metal ions with
DEHPA (1 M in kerosene) has been tested at dierent
pHs. The best results were obtained at pH 2:0 (extraction-Fe 100%, Zn 96%, Cu 6.5%). Zinc is stripped
from loaded organic phase by H2 SO4 (1 M) while iron
remains in the solvent phase being later stripped by HCl
solution (6 M).
It is consensual, that the main draw-backs in the use
of DEHPA as an iron extractant are related to the
stripping process (strong acid solutions required) and to
the low rate of extraction. In order to improve the latter,
Zhou et al. (1989) tried to use aqueous and organic
additives. They obtained satisfactory results )86.6% of

extraction in 10 min of contactwith a phosphorus

additive. In addition, they include a ow-sheet diagram
to recover selectively iron, indium, gallium and germanium from a leach solution (Fe 0.8 g/l, In 0.61.4 g/l, Ga
0.080.12 g/l, Ge 0.030.06 g/l, 2540 g/l of H2 SO4 ) at a
hydrometallurgical zinc plant. Firstly iron (9598%) and
indium are co-extracted with a mixture of 30% DEHPA/
700 ppm phosphorus additive in kerosene. The separation iron/indium is accomplished using dierent stripping solutions. The ranate, containing gallium and
germanium, is then treated in order to recover these
metals.
Prior (1991) described a complete and continuous
treatment of spent zinc galvanizing pickle liquors
(HCl 40 g/l) containing Fe (85 g/l) and Zn (56 g/l) with
DEHPA (20% in kerosene). In the rst stage, maintaining the pH between 4 and 5, almost all the iron and
zinc (ranate 20 ppm of Zn and about 760 ppm of Fe)
are removed from aqueous solution. The loaded organic
solvent is then contacted with fresh feed aqueous phase
at pH 1.42; this ensures no zinc stripping and the
substitution of ferrous ion in the solvent by zinc of the
aqueous solution. The separation between ferric ion and
zinc was achieved using selective stripping conditions,
rst a 25% of H2 SO4 solution to recover zinc and later a
6 N HCl solution to recover iron.
In the stripping process is not recommended to use
concentrated acid solution as it can degrade the organic
phase. Taking this into account and the fact that Fe2 is
readily stripped from DEHPA, a reduction of ferric ion
to ferrous ion can be one way to solve the problem.
Demopoulos and Gefvert (1984) reduced 8590% of
Fe(III) in loaded organic phase in 1 h at 165 C and
2500 kPa H2 . The Fe(II) present in the organic phase
(5 g/l) is then recovered by a dilute solution of sulphuric acid (88 g/l), under protective conditions to avoid
reoxidation of iron. Majima et al. (1985) carried out
studies on the reductive stripping of Fe3 -loaded DEHPA with water and several acids (HCl, HClO4 , H2 SO4 )
under a SO2 atmosphere. The results show that the
stripping reaction is favoured by high temperatures,
high pressures of SO2 and high concentrations of
H2 SO4 . The authors, using a T 343 K, 250 kPa SO2 ,
1.5 M H2 SO4 were able to remove in 30 min all iron
(1 102 M) from organic phase. These methods, which
use gaseous reductants (H2 and SO2 ), present as a disadvantage the high pressure and temperature required.
Lupi and Pilone (2000) studied the reductive stripping
of Fe3 from DEHPA in vacuum using zinc powder
as the reducing agent. They obtained a stripping yield
greater than 89% (Fe3
inic:;DEHPA 5 g/l) at room temperature and under 80 kPa of pressure. Sun and OKeefe
(2002) showed that steel scrap can be an eective reductant for ferric ion removal from DEHPA. Iron removal attained from loaded DEHPA (3.3 g/l Fe3 in
15% DEHPA, 4% TBP) was in the range 7582% for 10

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

The common feature in the use of such mixtures is

the possibility of using dilute solutions of sulphuric acid
(<1 M H2 SO4 ) to remove iron from loaded organic
phases.
Chen et al. (1992) and Shuqui et al. (1986) tested
dierent mixtures of extractants. Some of the best results published by these authors are summarised in the
Table 1.
These results show that is possible to use a dilute
solution of sulphuric acid (<1 M) to remove iron from a
loaded organic phase. Hoh et al. (1983) and Hirato et al.
(1992) also veried, respectively, the benet on iron
stripping by the addition of TBP or TOPO to DEHPA.
Xiquan et al. (1986) carried out a high pressure
leaching of zinc sulde concentrate under an oxygen
atmosphere and obtained a solution with Zn2 75 g/l,
Fe3 11 g/l. They used this solution to test the crossow extraction of Fe3 with a mixture of N-1923 (12%
v/v)/2-octanol(50% v/v)/kerosene and they achieved
good results i.e. >99% of extraction of iron (Zn in organic phase < 30 ppm) in 3 stages at A=O 1=0:6. The
stripping of the loaded organic phase containing 7.45 g
Fe l1 was accomplished with 0.5 N of H2 SO4 and an
aqueous/organic ratio of 1. The pH at equilibrium was
0.8 and the percentage of iron removed is about 60%.
Ismael and Carvalho (1996, 1999) and Ismael (1999)
studied the extraction of iron with a mixture of DEHPA/

0.3
H2SO4

0.2

0.092 M
0.153 M

3+

3.2. Synergistic mixtures

Primene JMT/2-octanol diluted in ShellSol T. Some of

the experiments were carried out with an aqueous solution containing 15 g/l of Fe3 and dierent mixtures of
the above extractants. Satisfactory results are achieved
with the mixture0.6 M DEHPA, 0.27 M Primene JMT,
0.63 M 2-octanol in ShellSol T which has a loading
capacity of 17 g.L1 (Ismael, 1999). An important
parameter on iron extraction is the concentration of acid
in the aqueous phase as it is shown in Fig. 1.
The results shown in Fig. 1 reveal that the increase in
acid concentration makes the extraction process dicult.
In Fig. 2 it is presented the equilibrium isotherm
curves for the stripping of loaded DEHPA and loaded
DEHPA/JMT mixture. From the analysis such gure it
is possible to conclude that a 0.25 M of H2 SO4 solution
is sucient to recover iron from a loaded DEHPA/JMT
mixture. When was used DEHPA alone it was not
possible to reduce the concentration of iron in the solvent to values lower than 0.1 M. Demopoulos and
Gefvert (1984) suggest that for an ecient recovery of

Fe org (M)

and 20 min of reaction. According to the authors one of

the advantages of this process is the possibility of obtaining pure iron by-products (electrolytic iron or cristallized ferrous sulphate). The disadvantage was in its
discontinuity.
Others approaches have been tried to overcome the
diculty on the DEHPA stripping, namely the use of
mixtures of extractants (synergistic mixtures).

35

0.204 M

0.1

0.306 M
0
0

0.1

0.2

0.3

0.4

3+
Fe aq (M)

Fig. 1. Equilibrium isotherm curves at dierent sulphuric acid concentration. Organic phase: DEHPA 0:60 M, JMT 0:27 M,
2-octanol 0:63 M in ShellSol T at T 298:15 K.

Table 1
Synergistic mixtures for iron extraction (Shuqui et al., 1986, Chen et al., 1992)
Aqueous solution

Organic solution
Extractant/diluent

Extraction
Additive

A:O

Stripping solution

Stripping
A:O

Fe 2.51 g/l, Al 54 g/l

pH 1.2

Primary amine (7.5%)

in n-octane

2-octanol

1:1

40
90

H2 SO4 0.3 M

2:1

<2
80

Fe3 2.21 g/l pH 1.57

Primary aminea (5%) in

n-octane

TRPO (1 M)
TOPO(0.4 M)
TBP(0.5 M)
TBP(1 M)

1:1

60
70
90
85
90

H2 SO4 0.15 M

1:1

25
70
60
50
60

DEHPA(10%), n-octane with Fe 4 g/l

Primary aminea (0.075 M)

pH 0.63

1:1

5
50

TRPOtrialkyl phosphine oxide (Rnumber of carbon atoms 810); TOPOtrioctyl phosphine oxide; TBPtributyl phosphate.
a
Primary amine(N1923) with a total number of carbon atoms of 1923 (molecular weight  293).

36

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

3.5. Carboxylic acid

0.4

DEHPA, JMT
0.60 M, 0.27 M

0.2

0.60 M

Fe

3+
aq (M)

0.3

0.1
0
0

0.1

0.2
Fe

3+
org

0.3

0.4

(M)

Fig. 2. Equilibrium isotherm curves for iron (III) stripping. Eect of

the addition of amine on Fe(III) stripping by sulphuric acid solution
(0.25 M). Organic phase: DEHPA 0:6 M, JMT 0:27 M,
2-octanol 0:63 M in ShellSol T at T 298:15 K.

iron from loaded DEHPA a solution of a 5 M H2 SO4 or

68 N HCl is necessary.
3.3. Amino-phosphoric acid extractants
The synthesis of new extractant molecules containing
an amino group and a phosphoric group (fused aminophosphoric acids; Delmas et al., 1996a; Delmas et al.,
1998) could be a solution to the problems of iron extraction. Delmas et al. (1996b) synthesised some extractants and pointed out that the most promising was
EU2 (phosphonomethylated alkylamine, R2 NCH2 PO(OH)2 , R
hydrocarbon). They achieved with EU2 high
Fe extractions (loading capacity about 15 g/l of Fe for
15% of EU2) and high selectivity over zinc (separation
factors Fe/Zn in the range 40005000). There are other
advantages such as the high partition coecient even at
high sulphuric acid concentration (40 g/l), fast phase
disengagement and the fact that the co-extraction of
other metals, especially zinc, is small. Relatively to
stripping process the results are not so interesting. In fact
it is not viable to reduce the iron in organic phase at
values lower than 67 g/l even with a 2 M of H2 SO4 solution (loaded organic phase, EU2 15% (v/v); Fe
13:5 g/l).
3.4. Amines
Other interesting works has been published on iron
extraction with amines by several researchers (Alguacil
and Amer, 1986; Alguacil et al., 1987; Mahi and Bailes,
1985). Juan and Perales (1994) leached zinc ferrites with
a sulphuric acid solution in order to dissolve all zinc
and iron. The primary amine (Primene 81Room and
Haas) was used to extract iron from the leach solution.
Iron was then precipitated from the organic phase with
an aqueous solution of ammonium sulphate/ammonia.
The aqueous phase was ltered and the iron residue was
then calcined to obtain iron oxide.

Carboxylic acids have been reported, since the early

1960s as iron extractants alternatives to alkyl phosphoric acids (Van der Zeeuw, 1979; Stefanakis and
Monhemius, 1983, 1985, 1987; Preston, 1985). Their
advantages include good thermal stability, low cost and
high selectivity for iron (III) over other base metals.
However the use of such extractants was compromised
since a precise pH control was required (Fletcher et al.,
1964; Thorsen et al., 1984).
Thorsen (1977) and Thorsen et al. (1984) developed a
slightly dierent approach to remove iron in zinc hydrometallurgy with a tertiary carboxylic acid (Versatic
Acid); this process is known as the Versatic Acid
Process. In this process the zinc calcine is directly leached with the organic phase (Versatic acid). The reaction is given by the equation:
ZnOs 2RHorg $ R2 Znorg H2 O
where RH represents the Versatic acid. The leach residue, mainly zinc ferrite, is attacked by the acid in order
to dissolve the zinc and the iron. Iron in the acidic solution is then extracted with the zinc-loaded organic
phase; in this step there is an ion exchange of zinc for
iron, according to the reaction:
2
3ZnR2;org 2Fe3
aq $ 2FeR3 3Znaq

The aqueous phase containing only zinc is sent to the

electrolysis. The stripping of loaded organic phase can
be performed in dierent ways: hydrolytic stripping,
precipitation stripping and carboxylic acid stripping. In
hydrolytic stripping (Monhemius et al. 1984, 1993;
Monhemius and Doyle-Garner, 1985) the loaded organic phase is heated together with water at 150200 C,
leading to the iron precipitation as hematite. The main
drawback of this process is the diculty in the separation of the solid phase from the organic phase and the
fact that the solid has no pigment quality (Collier et al.,
1986). In precipitation stripping, the stripping phase is a
dilute solution of a mineral acid and the precipitation
can be carried out at temperatures below the boiling
point of water. However, the problems mentioned in
hydrolytic stripping remain. Collier et al. (1986) tried to
remove iron from Versatic acid by acid formic stripping.
In order to minimize the acid formic losses, the solid
phase was washed with water. The solution obtained is
very diluted and need to be concentrated by evaporation. This step makes the overall process very expensive;
Collier et al. (1986) point out that it becomes 30% more
expensive than the conventional jarosite process.
4. Conclusions
Most of the worlds zinc producers currently use the
jarosite process to remove iron from the aqueous solu-

M.R.C. Ismael, J.M.R. Carvalho / Minerals Engineering 16 (2003) 3139

tion because of its simplicity and low costs. However,

large amounts of residues are produced and stockpiled
in various types of storage ponds and lately this practice
has become questionable on environmental grounds.
The production of a marketable product (hematite)
has been carried out at least in two electrolytic plants to
overcome the jarosite waste disposal problem, since
hematite is sold to cement makers. The use of such hematite in the steel industry is not allowed because it is
not totally free of contaminants (Zn, As, Ga, Ge, etc.).
In order to obtain a clean hematite, iron must be precipitated from pure solutions. Pure ferric solutions could
be obtained by solvent extraction techniques if selective
extractants are used.
The classes of organophosphoric and carboxylic acids
extractants present a high anity to ferric ions. However, the use of these extractants is not advisable due to
problems related to the stripping process. In fact the
stripping of a loaded solvent could be only accomplished
using high concentrations of sulphuric acid or using
sophisticated methods such as reductive or hydrolytic
stripping.
Recently, interesting results in iron extraction with
mixtures of extractantssynergistic mixtures have been
published. The most promising are mixtures of aminealquil phosphoric acid and amine and 2-octanol. It is
possible to carry out the stripping of these loaded solvents using a weak acid solution.
In the future the recovery of iron by the solvent
extraction technique will certainly involve the use of
synergistic mixtures unless new iron extractants are
synthesized.

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