Two-stage Countercurrent Solvent Extraction of Copper from Cuprous
Chloride Solution: Cu(II) Loading Coupled with Cu(I) Oxidation by Oxygen
and Iron Scrubbing

Jianming Lu, David Dreisinger

PII: S0304-386X(14)00188-1
DOI: doi: 10.1016/j.hydromet.2014.09.003
Reference: HYDROM 3951

To appear in: Hydrometallurgy

Received date: 22 May 2014

Revised date: 6 September 2014
Accepted date: 8 September 2014

Please cite this article as: Lu, Jianming, Dreisinger, David, Two-stage Countercurrent
Solvent Extraction of Copper from Cuprous Chloride Solution: Cu(II) Loading Cou-
pled with Cu(I) Oxidation by Oxygen and Iron Scrubbing, Hydrometallurgy (2014), doi:
10.1016/j.hydromet.2014.09.003

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 ACCEPTED MANUSCRIPT

Two-stage Countercurrent Solvent Extraction of Copper from

Cuprous Chloride Solution: Cu(II) Loading Coupled with Cu(I)
Oxidation by Oxygen and Iron Scrubbing

Jianming Lu and David Dreisinger,

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Department of Materials Engineering, University of British Columbia,
309-6350 Stores Road, Vancouver, BC, Canada, V6T 1Z4

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Abstract

This study was conducted as part of the development of a novel process for copper

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recovery from copper sulfide concentrates by chloride leaching, simultaneous cuprous
oxidation and cupric solvent extraction to transfer copper to a conventional sulfate
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electrowinning circuit and hematite precipitation to reject iron. Four LIX reagents
(LIX84-I, LIX612N-LV, XI-04003 and LIX984N) were used as extractants while
kerosene was used as a diluent. Copper was effectively extracted into LIX reagent
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organic solution from chloride solution. However, iron co-extraction exceeded 0.5 g/L.
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Two-stage countercurrent solvent extraction is proposed to reduce iron extraction. In the

first stage, copper-loaded organic solution was pre-scrubbed by contacting with the
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cuprous and ferrous chloride pregnant leach solution. The extent of iron removal
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increased from 78 to 91 to 95% with decreasing pH from 1.0 to 0.5 to 0.0 while the
extent of copper removal increased from 1 to 17 to 36%. Although more iron was
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removed at a pH below 0.5, copper was removed to an unacceptable level. Therefore, it is

recommended that pH should be controlled around 1.0 to remove the bulk of the loaded
iron while avoiding excessive copper stripping. In the second solvent extraction stage,
copper is loaded into the organic solution by simultaneous cuprous oxidation by oxygen
and cupric extraction. After two-stage counter current solvent extraction, the organic
solution was further scrubbed by contacting with copper sulfate (4 g/L Cu) and sulfuric
acid (15 g/L) solution. The iron extraction was reduced to a satisfactory level at an A/O
ratio of 1/40 to 1/20 while the copper extraction practically did not change. The Cu/Fe
ratio in copper-loaded organic solution can meet the industrial requirement.

Keywords: Copper; Solvent extraction; Chloride solution; Iron removal

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1. Introduction

Ferric and/or cupric chloride leaching processes have been extensively studied to treat
sulfide concentrates of copper, lead and zinc (Dutrizac, 1992; Peters, 1977). Chloride
leaching has several advantages over sulfate systems: (1) supporting high metal

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solubility, (2) enhanced redox behaviour, (3) increased rates of leaching and (4) the

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formation of predominantly elemental sulfur. In a chloride system, both cuprous and
cupric ions are stabilized through complexation with chloride ions. Copper can be

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efficiently extracted into chloride solution from chalcopyrite concentrates and a copper
extraction of 99% can be reached at a temperature below 100 C using a two-stage

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countercurrent chloride leach circuit (Lu and Dreisinger, 2013a and 2013b). Compared to
the conventional sulfate system, one challenge for the chloride system is to produce high
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quality copper since some impurities such as silver are not removed efficiently from
chloride solution and dendritic copper cathodes are produced by electrowinning from
chloride solution. The high surface area dendrites are difficult to wash to remove surface
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contamination.
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Generally there are four processes to recover copper from chloride solution: (1) the
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precipitation of CuCl at lower temperature and reduction to Cu in the UBC-Cominco and

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the Cymet processes (Durtrizac, 1992; Peters, 1977), (2) direct electrowinning of Cu
from chloride solution (Moyes et al., 2000), (3) the precipitation of Cu2O and reduction
to Cu with hydrogen (Hyvarinen and Hamalainen, 2005) and (4) solvent extraction of
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copper in to a sulfate system from chloride system and electrowinning of copper from
sulfate media (Demarthe et al.,1976; Liddicoat and Dreisinger, 2007). The first two
methods may result in impure copper (such as contamination with silver) while the third
one is generally suitable for leach solution containing a small amount of iron and other
impurities. The fourth one can generate high purity copper since the impurities are
separated from copper by solvent extraction.

With the use of solvent extraction to transfer copper to a conventional sulfate

electrowinning circuit from a chloride leaching system, the advantages of the chloride
leaching system can be well utilized. The transfer of copper from a Cu(I) chloride
solution to a Cu(II) sulfate solution requires extraction with a hydroxyoxime extractant

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(HR) as is used normally in the processing of sulfate-based copper leach solutions. The
solvent extraction process for copper recovery involves simultaneous cuprous oxidation
by oxygen and cupric solvent extraction:

4CuCl + 4HR(org) + O2 = 2CuR2(org) + 2CuCl2 + 2H2O (1)

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Half of the copper in aqueous solution is extracted into organic solution.

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Conveniently, the remaining copper as cupric chloride in the raffinate from solvent
extraction serves as a leaching agent upon recycle.

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Four LIX extractants (LIX84-I, LIX612N-LV, XI-04003 and LIX984N) from BASF

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were tested since they have a high selectivity for copper over iron. LIX 84-I is formulated
with a C9 ketoxime. LIX 984N is a 50:50 mixture of LIX 860N-I (C9 aldoxime) with
LIX 84-I. XI04003 is formulated with a C12 aldoxime and LIX 612N-LV is formulated
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with a C9 aldoxime. Both are formulated with a ketone as a modifier to the same degree
of modification. If properly formulated, they should give identical performance within
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the limits of error of the experiment.

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Copper can effectively be extracted into organic solution containing the above four
LIX reagents from copper chloride solution with minimum transfer of impurities (Lu and
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Dresinger, 2013c, 2013d). However, the final iron extraction after the extraction of half
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of the copper from chloride solution reached an unacceptable level, which can
significantly affect copper electrowinning from sulfate media. Therefore the iron
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extraction must be decreased. A typical ratio of Cu/Fe in copper-loaded organic phase

exceeds 500 in normal solvent extraction practice. The co-loading of iron with copper is
a result of Reaction 2 below.

4FeCl2 + 6HR(org) + O2 = 2FeR3(org) + 2FeCl3 + 2HCl + 2H2O (2)

Two-stage countercurrent solvent extraction is proposed to reduce iron extraction. In

the first stage, no oxygen is introduced. Copper-loaded organic phase is pre-scrubbed by
contacting with pregnant cuprous and ferrous leach solution to remove iron. In the second
stage, oxygen is introduced to load copper into organic solution. The oxidative loading
of copper (and iron) is shown in Reactions 1 and 2 and the removal of iron (and possibly
some copper) in the countercurrent scrubbing process is shown in the reactions below.

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FeR3 (org) + CuCl + HCl = FeCl2 + CuR2(org) + HR(org) (3)

CuR2(org) + 2HCl = CuCl2 + 2HR(org) (4)

After solvent extraction, copper-loaded organic solution must be washed to remove

entrained aqueous solution and especially prevent the transfer of excess chloride to

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electrowinning. Washing solution can be made by mixing copper sulfate electrolyte and

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water (Virnig and Fisher, 2003). A typical wash solution composition contains around 15
g/L H2SO4 and 3-4 g/L Cu. When the washing solution is contacted with copper-loaded

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organic solution, iron can further be scrubbed.

The objective of this study is to find a way to minimize iron extraction during copper

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solvent extraction and effectively scrub iron from copper-loaded organic solution. This
study was necessary for the development of a novel process for copper recovery from
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chalcopyrite concentrates by chloride leaching, simultaneous cuprous oxidation and
cupric solvent extraction to transfer copper to a conventional sulfate electrowinning
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circuit and hematite precipitation to reject iron.

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2. Experimental
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2.1. Apparatus
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Copper loading was conducted in a 400-mL glass reactor with three glass baffles and
a rubber stopper fitted with a sleeve to house an impeller, a gas dispersion tube, a pH
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probe and other openings (Fig. 1). The reactor was placed in a water bath and the
temperature was maintained at 400.2 C. The temperature of pregnant leaching solution
can be as high as 90C. At a higher temperature, the solvent extraction is faster and the
organic solution is less viscous. However the organic reagent degrades rapidly at a
temperature above 40C. If the solvent extraction is conducted below 40C, the leaching
solution has to be cooled down at an additional cost. Therefore 40 C was selected for
this study. The titanium stirrer was made of 5-mm diameter rod with a 25-mm diameter
45 pitched blade impeller and was driven via overhead motors.

Scrubbing loaded organic solution using ferrous and cuprous chloride solution was
also conducted in the reactor shown in Fig. 1 under a nitrogen environment without the

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use of an oxygen gas sparger. Scrubbing loaded organic using copper sulfate and sulfuric
acid solution was conducted manually in a separatory funnel.

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Sampling hole N
2
Air/O2
pH probe

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Ti shaft
Baffle Baffle

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Gas sparger Ti impeller
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Fig. 1 A schematic diagram of the glass reactor for oxidation-solvent extraction

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2.2. Experimental Procedures

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The procedures for copper loading are:

(1) A required amount of organic solution is added into the reactor and it is then purged
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with nitrogen gas.

(2) The pregnant cuprous and ferrous chloride solution is transferred to the reactor under
a nitrogen atmosphere.

(3) The mixture of aqueous and organic solutions is stirred and then air or oxygen is
introduced to the reactor.

(4) The pH is monitored and recorded and the sample is taken using a syringe.

(5) The sample is centrifuged to separate aqueous and organic phases.

(6) The organic and aqueous samples are taken for analysis using a pipette.

(7) The final aqueous and organic solutions were separated using a separatory funnel.

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The procedures for pre-scrubbing copper-loaded organic solution using pregnant

cuprous and ferrous chloride solution:

(1) A required amount of copper-loaded organic solution is added into the reactor and it
is then purged with nitrogen gas.

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(2) The pregnant cuprous and ferrous solution is transferred to the reactor under a

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nitrogen atmosphere.

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(3) The mixture of aqueous and organic solutions is stirred and the pH is adjusted to a
target value by addition of sulfuric acid solution.

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(4) The mixture is transferred to a separatory funnel to separate the aqueous and organic
solutions. MA
(5) The aqueous solution is filtered using Whatman No. 3 filter paper to remove entrained
organic solution while the organic solution is filtered using Whatman 1PS filter paper to
remove entrained aqueous solution.
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The procedures for scrubbing copper-loaded organic phase using copper sulfate and
sulfuric acid solution are:
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(1) A required amount of copper-loaded organic solution and copper sulfate and sulfuric
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acid solution are added into a separatory funnel.

(3) The mixture of aqueous and organic solution is stirred using a magnetic stirring bar
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driven by a magnetic stirrer for 30 minutes to ensure that the scrubbing reactions reach
their equilibriums.

(4) After the aqueous and organic solutions are separated, the aqueous solution is filtered
using Whatman No. 3 filter paper to remove entrained organic solution while the organic
solution is filtered using Whatman 1PS filter paper to remove entrained aqueous solution.

(5) The organic samples are stripped three times using 6M HCl solution. All the strip
solutions are collected for chemical analysis.

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2.3. Preparation of Organic and Aqueous Solution

Organic solutions were prepared on a volume basis (40% extractant and 60% Phillips
66 kerosene). The aqueous feed solution for cuprous oxidation and cupric solvent
extraction was prepared by the following procedures:

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(1) The reagent grade calcium chloride is first dissolved in deionized water in a beaker

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and then half of the required amount of reagent grade cupric chloride and a required
amount of reagent grade ferrous chloride are added into the beaker. The beaker is then

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sealed and purged with argon.
(2) An excess amount of metallic copper powder is added into the beaker and then the

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solution is stirred at 80-90 C until it becomes transparent with a greenish color. This
procedure is used to ensure that all copper and iron are present in the cuprous and ferrous
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oxidation states in the starting solution.

2.4. Chemical Analysis

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The concentrations of Cu (raffinate, strip and washing solutions) and Fe (raffinate and
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washing) were analyzed using atomic absorption spectrometry.

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3. Results and Discussion

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Cuprous oxidation and cupric solvent extraction can be expressed by the following
reactions:
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2Cu+ + 1/2O2 + 2H+ = 2Cu2+ + H2O (5)

Cu2+(aq) + 2HR(org) = CuR2(org) + 2H+(aq) (6)

Copper solvent extraction from cuprous chloride solution is determined by cuprous

oxidation by oxygen. Not only is Cu(I) oxidized but also Fe(II) is oxidized since the
redox potential for Cu(II)/Cu(I) is close to that for Fe(III)/Fe(II) due to a high chloride
concentration (Lu and Dreisinger, 2013d; Muir and Senanayake, 1984; Winand, 1991).
Therefore ferrous oxidation and ferric solvent extraction take place as the minor
reactions:

2Fe2+ + 1/2O2 + 2H+ = 2Fe3+ + H2O (7)

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Fe3+(aq) + 3HR(org) = FeR3 (org) + 3H+(aq) (8)

3.1. Copper Loading by Cupric Extraction Coupled with Cuprous Oxidation by Oxygen

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In the copper loading stage, oxygen was introduced to oxidize cuprous to cupric ions
for copper solvent extraction (Reactions 5 and 6). Ideally half of the copper in aqueous

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solution are extracted into organic solution as indicated by Reaction 1. Therefore the A/O
ratio was set at such a value that half of the copper was extracted from the aqueous

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solution. The plots of copper extraction and pH against the total Cu(I) and Fe(II) oxidized
or total Cu(II) and Fe(III) produced (called the total [Cu(II) + Fe(III)]) are shown in Fig.

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2. The results for XI-04003 were nearly identical to that for LIX612N-LV as expected.
Therefore they are not given in Fig. 2. According to the change in pH, copper solvent
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extraction can be divided into three regimes. In Regime 1, the pH decreased rapidly. The
acid produced due to copper and iron solvent extraction (Reactions 6 and 8) was greater
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than that consumed due to cuprous and ferrous oxidation (Reactions 5 and 7). The net
acid produced ([HCl]) and copper extracted ([Cu]ex) in molarity can be expressed as
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follows:
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[HCl] = 2[Cu]ex + 3[Fe]ex - total [Cu(II) + Fe(III)] (9)

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[Cu]ex = 1/2(total [Cu(II) + Fe(III)] + [HCl] -3[Fe]ex) (10)

where [Fe]ex is the iron extracted in molarity. The acid released due to the iron extraction
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(3[Fe]ex) was much less than the net acid produced ([HCl]). Therefore the copper
extracted (in molarity) was more than half of the total [Cu(II)+Fe(III)]. The slope of the
copper extraction curve was the highest in Regime 1 (a total [Cu(II) + Fe(III)] of 0 to
~0.22 M). The slope of the curve for LIX984N was higher than that for LIX612N-LV
while the pH for LIX984N was lower than that for LIX612N-LV since LIX984N has a
greater extractant strength than LIX612N-LV.

In Regime 2 (a total [Cu(II) + Fe(III)] of 0.22 to 0.31 M for LIX612N-LV and 0.35 M
for LIX984N), the acid production due to copper and iron solvent extraction was equal to
the acid consumption due to cuprous and ferrous oxidation. The acid concentration
reached a maximum value and remained constant (as evidenced by the pH reaching a

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minimum value and staying constant). The minimum pH values for LIX984N and
LIX612N-LV were -0.33 and -0.29 respectively. The activity coefficient of H+ in the
aqueous solution of this study is very high and the measured pH of the aqueous solution
containing 0.03M HCl was about -0.3. Therefore only a very amount of net acid was

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produced. Since the net acid production was nearly zero and the iron extraction increased,
the slope of the curve for copper extraction decreased slightly.

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In Regime 3 (a total [Cu(II) + Fe(III)] of above 0.31M for LIX612N-LV and 0.35 M for

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LIX984N), as the extraction of copper and iron approached their full extent of loading,
the sum of copper and iron extractions increased at a decreasing rate. The acid

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production due to copper and iron solvent extraction was less than the acid consumption
due to the cuprous and ferrous oxidation. The acid concentration decreased and the pH
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increased. The slope of the curve for copper extraction decreased faster as the overall rate
of metal extraction decreased and the iron extraction increased. The slope of the curve for
LIX984N decreased faster than that for LIX612N-LV since LIX984N has a lower
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selectivity of copper over iron than LIX612N-LV and the iron extraction for LIX984N
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increased much faster than that for LIX612N-LV.

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As shown in Fig. 3, with increasing total [Cu(II) + Fe(III)], the iron extraction
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initially increased slowly and then quickly as the aqueous solution pH and ferric
concentration increased. At a total [Cu(II) + Fe(III)] of 0.3M, the iron extractions for
LIX612N-LV and LIX984N were 0.008 and 0.085 g/L respectively. With increasing total
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[Cu(II) + Fe(III)] to 1.2 M, the iron extractions for LIX612N-LV and LIX984N increased
0.4 and 0.6 g/L respectively. At a total [Cu(II) + Fe(III)] above 1.2 M, the iron extraction
for LIX984N increased much faster than that of LIX612N-LV and the iron extractions for
both extractants became significant. The Cu/Fe ratio in the organic solution of LIX984N
was first maintained at 64 and then decreased slowly to 15 while that for LIX612N-LV
first decreased rapidly from about 600 to 110 and then slowly to 40. The selectivity of
copper over iron for LIX612N-LV was higher than those for LIX984N under the
conditions of this study.

As indicated by Reaction 1, the target total [Cu(II) + Fe(III)] is the initial cuprous
concentration (1.25 M). At this target total [Cu(II) + Fe(III)], the iron extraction and the

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Cu/Fe ratio for LIX612N-LV were about 0.5 g/L and 40 respectively while those for
LIX984N were about 0.8 g/L and 25 respectively. The iron extraction was so high that
iron had to be removed before contacting with copper electrolyte for copper stripping.
Therefore the copper-loaded organic phase was scrubbed in the first solvent extraction

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stage to remove the bulk of the extracted iron.

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25 1.2
Cu (LIX612N-LV)
Cu (LIX984N)

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20
Metal Extraction / g/L -1

0.8
pH (LIX612N-LV)
15 pH (LIX984N)
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pH
0.4
10
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0.0
5
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0 -0.4
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0 0.3 0.6 0.9 1.2 1.5

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Total [Cu(II) and Fe(III)] / M

Fig. 2 Copper extraction and pH as a function of total [Cu(II) + Fe(III)] at 40 C. A/O

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ratios: 1.98 for LIX984N and 2.01 for LIX612N-LV. Aqueous feed solution: 1.25 M
CuCl + 2 M FeCl2 + 1.5M CaCl2.

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1.5 700
Fe (LIX612N-LV)
Fe (LIX984N) 600
1.2
Cu/Fe (LIX612N-LV)
-1
500
Fe extraction / g L

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Cu/Fe (LIX984N)

Cu/Fe ratio
0.9
400

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300
0.6

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200
0.3
100

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0.0 0
0 0.3 0.6
MA 0.9 1.2 1.5
Total [Cu(II) + Fe(III)] / M

Fig. 3 Iron extraction and Cu/Fe ratio as a function of total [Cu(II) + Fe(III)] at 40 C.
A/O ratios: 1.98 for LIX984N and 2.01 for LIX612N-LV. Aqueous feed solution: 1.25 M
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CuCl + 2 M FeCl2 + 1.5M CaCl2.

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3.2. Scrubbing Loaded Organic Solution Using Pregnant Cuprous and Ferrous Chloride
Solution
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In the first solvent extraction (or scrubbing) stage, no oxygen was introduced.
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Copper-loaded organic phase was scrubbed by contacting with pregnant cuprous and
ferrous chloride leach solution to remove iron. The A/O ratio for scrubbing was the same
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as that for copper loading as discussed in the previous section. The plots of the copper
and iron removal and the Cu/Fe ratio against the number of scrubbing steps at different
pHs for LIX612N-LV are shown in Fig. 4. The iron removal was determined by pH and
only slightly affected by the number of scrubbing steps. By increasing number of
scrubbing steps from 1 to 3, the iron removal increased only from 78.0 to 80.4% (at pH
1.0), 90.8 to 93.8% (at pH 0.5) and 94.5 to 95.3% (at pH 0.0). The copper removal was
mainly determined by pH and also affected by the number of scrubbing steps to some
extent. By increasing the number of scrubbing steps from 1 to 3, the copper removal
increased from 1.0 to 2.4% (at pH 1.0), 16.5 to 28.5% (at pH 0.5) and 35.5 to 56.9% (at
pH 0.0). At a lower pH, more copper was removed and the copper removal increased
faster with increasing number of scrubbing steps. The Cu/Fe ratio increased from 25

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(initial) to 115 to 123 to 131 (at pH 1.0) and from 19 (initial) to 167 to 178 to 213 (at pH
0.50), while at pH 0.0, it first increased from 20 (initial) to 231 and then decreased to 193
to 178 because the copper removal increased quickly with increasing number of
scrubbing steps.

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The copper and iron removals and Cu/Fe ratio at pH 0.50 for XI-04003 are shown in

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Fig. 5. The degree of iron removal increased only from 87.9 to 90.2% with increasing
number of scrubbing steps from 1 to 3 while the copper removal increased from 14.4 to

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23.4% and the Cu/Fe ratio increased from 22.4 (initial) to 158 to 160 to 176.

The removals of copper and iron at pH 0.50 for LIX984N are summarized in Fig. 6.

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The iron removal increased from 91.5 to 94.0% with increasing number of scrubbing
steps from 1 to 3 while the copper removal increased almost linearly from 6.5 to 21.1%.
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The Cu/Fe ratio increased from 13.2 (initial) to 146 to 160 to 176. The results for
scrubbing at pH 0.50 are similar to those for LIX612N and XI-04003. It is expected that
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the scrubbing results at pH 1.0 or 0.0 for XI-04003 and LIX982N are very similar to
those for LIX612N-LV.
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In all cases, iron was removed significantly in the first scrubbing step and slightly
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with further scrubbing. In the first scrubbing step, the iron concentration decreased to
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such a low value that iron became more difficult to remove than copper. More copper and
less iron were removed with successive scrubbing. The concentrations of iron and copper
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and then the removal of copper and iron were determined by the distribution equilibriums
of copper and iron (Reactions 6 and 8) and they were dependent on pH and type of
extractant as shown in Table 1. To minimize the significant removal of copper from the
organic phase, scrubbing should be conducted at a pH above 0.5. A single scrubbing
stage should be enough because further scrubbing improves iron removal slightly and
increases copper removal significantly.

With increasing chloride concentration, the redox potential for Cu(II)/Cu(I) increases
while the redox potential for Fe(III)/Fe(II) decreases due to their different chloro-
complex formation constants (Muir and Senanayake, 1984; Winand, 1991). Therefore a
lower chloride concentration results in a higher [Cu(II)/Fe(III)] ratio in aqueous solution
as expected from the Nernst equation and then a higher Cu/Fe ratio in organic solution. A

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lower calcium chloride concentration should be used to reduce the iron extraction during
copper loading and facilitate the iron removal during scrubbing.

Table 1 Cu and Fe extraction after scrubbing once using pregnant ferrous and cuprous
solution at an O/A ratio of 1.9

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Extractants pH Cu / g L-1 Fe / g L-1
LIX612N-LV 1.0 20.8 0.18
LIX612N-LV 0.5 17.7 0.11

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LIX612N-LV 0.0 13.6 0.06
XI-04003 0.5 17.9 0.11

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LIX984N 0.5 20.3 0.14

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Cu, pH1.0 Fe, pH 1.0 Cu, pH 0.5
Fe, pH 0.5 Cu, pH 0.0 Fe, pH 0.0
Cu/Fe, pH 1.0 Cu/Fe, pH 0.5 Cu/Fe, pH 0.0
100 250
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80 200
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Metal removal / %

Cu/Fe ratio
60 150
P

40 100
CE

20 50
AC

0 0
0 1 2 3 4
Number of scrubbing step
Fig. 4 Removal of copper and iron and Cu/Fe ratio vs number of scrubbing steps at
different pHs for LIX612N-LV. The copper and iron concentrations of the organic feed
solution: 21.0 g/L Cu and 0.83 g/L Fe for pH 1.0; 21.2 g/L Cu and 1.2 g/L Fe for pH 0.5;
and 21.1 and 1.1 g/L Fe for pH 0.0. The composition of aqueous solution: 1.25 M (101
g/L) Cu as CuCl + 2 M (112 g/L) Fe as FeCl2 + 1.5M (166 g/L) CaCl2.

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100 200

80 160
Metal removal / %

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60 Cu, pH 0.5 120

Cu/Fe
Fe, pH 0.5

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Cu/Fe, pH 0.5
40 80

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20 40

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0 0
0 1 MA 2 3 4
Number of scrubbing step
Fig. 5 Removal of copper and iron and Cu/Fe ratio vs number of scrubbing steps at pH
0.50 for XI-04003. The copper and iron concentrations of the organic feed solution: 21.7
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g/L Cu and 0.93 g/L Fe. The composition of aqueous solution: 1.25 M (101 g/L) Cu as
CuCl + 2 M (112 g/L) Fe as FeCl2 + 1.5M (166 g/L) CaCl2.
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100 200
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CE

80 160
Metal removal / %

Cu/Fe ratio
60 120
AC

Cu, pH 0.5
Fe, pH 0.5
40 Cu/Fe, pH 0.5 80

20 40

0 0
0 1 2 3 4
Number of scrubbing step
Fig. 6 Removal of copper and iron and Cu/Fe ratio vs number of scrubbing steps at pH
0.50 for LIX984N. The copper and iron concentrations of the organic feed solutions: 21.0
g/L Cu and 1.6 g/L Fe. The composition of aqueous solution: 1.25 M (101 g/L) Cu as
CuCl + 2 M (112 g/L) Fe as FeCl2 + 1.5M (166 g/L) CaCl2.

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3.3. Scrubbing Copper- Loaded Organic Solution Using Diluted Copper Sulfate and
Sulfuric Acid Solution
In the scrubbing stage of two-stage countercurrent solvent extraction, iron was not
removed to a satisfactory level using ferrous and cuprous chloride solution. Copper-

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loaded organic solution was further scrubbed using a mixture of copper electrowinning
electrolyte bleed (10%) and water (90%). The composition of scrubbing solution used in

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this study was 15 g/L sulfuric acid and 4 g/L Cu. The copper and iron extractions after
further scrubbing are summarized in Tables 2 to 6. The organic feed solution for Table 2

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(LIX612N-LV) was pre-scrubbed at pH 0.5 using ferrous and cuprous chloride solution.
Scrubbing using the above sulfuric acid and copper sulfate solution was very effective. A

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higher A/O ratio resulted in the removal of more iron. At A/O ratios of 1/10 and 1/20, the
iron concentrations were reduced to less than 0.007 and 0.012 g/L respectively and the
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Cu/Fe ratios exceeded 2486 and 1442 respectively. At an A/O ratio of 1/40, the iron
concentration was reduced to 0.021 g/L and the Cu/Fe ratio increased to 823 in the first
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scrubbing step. The iron concentration was further reduced to less than 0.009 g/L and the
Cu/Fe ratio exceeded 1933 in the second scrubbing step. The copper loading increased
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slightly after scrubbing due to the extraction of copper from the scrubbing solution to the
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organic solution.
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The organic feed solution for Table 3 (LIX612N-LV) was pre-scrubbed using
cuprous and ferrous chloride solution at pH 1.0. The A/O ratio was set at 1/80. With
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scrubbing twice, the iron concentration decreased from 0.162 to 0.051 to 0.021 g/L and
the Cu/Fe ratio increased from 125 to 390 to 933 while the copper loading only
decreased by 0.2 g/L.

The organic solution for Table 4 (LIX612N-LV) was not pre-scrubbed using ferrous
and cuprous chloride solution and therefore the iron concentration was high. By
scrubbing at an A/O ratio of 1/20 twice, the iron concentration decreased from 0.561 to
0.021 g/L and the Cu/Fe ratio increased from 37 to 985. An A/O ratio of 1/20 or higher is
needed to remove iron to an acceptable level from the organic solution not pre-scrubbed
using cuprous and ferrous chloride solution. Copper extraction virtually did not change
after scrubbing.

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The scrubbing results for the XI-04003 organic solution (pre-scrubbed using ferrous
and cuprous solution at pH 0.50) are given in Table 5. After scrubbing at an A/O ratio of
1/40 twice, the iron concentration decreased from 0.092 to less than 0.010 g/L and the
Cu/Fe ratio increased from 191 to more than 1780 while the copper loading increased by

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0.2 g/L. The scrubbing results for XI-04003 are very close to those for LIX612N-LV as
expected.

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The scrubbing results for the LIX984N organic solution (pre-scrubbed using ferrous

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and cuprous solution at pH 0.5) are summarized in Table 6. After scrubbing at an A/O
ratio of 1/40 twice, the iron concentration decreased from 0.128 to 0.035 g/L and the

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Cu/Fe ratio increased from 157 to 580 while the copper loading increased by 0.2 g/L.
Iron was more difficult to scrub out of LIX984N organic solution than those of
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LIX612N-LV possibly due to its lower selectivity of copper over iron.

Table 2 Copper and iron extractions after scrubbing the organic solution pre-scrubbed at
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pH 0.5 using cuprous and ferrous chloride solution (LIX612N-LV)

Elements or Cu/Fe ratio Cu / g L-1 Fe / g L-1 Cu/Fe ratio
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Organic feed 17.2 0.095 181

A/O ratio = 1/10 One step scrubbing 17.4 < 0.007* > 2486
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A/O ratio = 1/20 One step scrubbing 17.3 < 0.012* > 1442
A/O ratio = 1/40 1 st scrubbing step 17.3 0.021 823
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2 nd scrubbing step 17.4 <0.009* > 1933

*Estimated based on the mass balance since the concentration in strip solution (6M HCl)
was below its ICP detection limit.
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Table 3 Copper and iron extractions after scrubbing the organic solution pre-scrubbed at
pH 1.0 using cuprous and ferrous chloride solution (LIX612N-LV)
Elements or Cu/Fe ratio Cu / g L-1 Fe / g L-1 Cu/Fe ratio
Organic feed 20.2 0.162 125
A/O ratio = 1/80 1 st scrubbing step 20.1 0.051 390
2 nd scrubbing step 20.0 0.021 933

Table 4 Copper and iron extractions after scrubbing the organic solution without pre-
scrubbing (LIX612N-LV)
Elements or Cu/Fe ratio Cu / g L-1 Fe / g L-1 Cu/Fe ratio
Organic feed 20.9 0.561 37
A/O ratio = 1/20 1 st scrubbing step 20.8 0.069 301
2 nd scrubbing step 20.7 0.021 985

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Table 5 Copper and iron extractions after scrubbing the organic solution pre-scrubbed at
pH 0.5 using cuprous and ferrous chloride solution (XI-04003)
Elements or Cu/Fe ratio Cu / g L-1 Fe / g L-1 Cu/Fe ratio

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Organic feed 17.6 0.092 191
A/O ratio = 1/40 1 st scrubbing step 17.7 0.021 842
2 nd scrubbing step 17.8 <0.010* > 1780

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*Estimated based on the mass balance since the concentration in strip solution (6M HCl)
was below its ICP detection limit.

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Table 6 Copper and iron extractions after scrubbing the organic solution pre-scrubbed at
pH 0.5 using cuprous and ferrous chloride solution (LIX984N)

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Elements or Cu/Fe ratio Cu / g L-1 Fe / g L-1 Cu/Fe ratio
Organic feed 20.1 0.128 157
A/O ratio = 1/40 1 st scrubbing step 20.2 0.049 412
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2 nd scrubbing step 20.3 0.035 580
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4. Conclusions
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Two-stage countercurrent solvent extraction should be used to extract copper from

cuprous chloride solution. In the first stage, copper-loaded organic is pre-scrubbed by
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contacting with pregnant cuprous and ferrous chloride solution while in the second stage,
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oxygen is introduced to oxidize cuprous to cupric ions for copper loading. At pH 1.0,
78% of the iron was removed from the copper-loaded organic solution during pre-
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scrubbing while copper was only removed by 1%. Iron was only removed slightly with
further pre-scrubbing using cuprous and ferrous chloride solution. At pH 0.5 and 0.0,
more iron was removed. However, copper was removed to an unacceptable level.
Therefore pH should be controlled around 1.0. In order to decrease iron extraction during
copper loading and facilitate the iron removal during pre-scrubbing, a low calcium
chloride concentration should be used.
After the copper-loaded organic solution was further scrubbed using copper sulfate
and sulfuric acid solution at an A/O ratio of 1/40 to 1/20, iron was removed to a
satisfactory level and the copper extraction virtually remained constant. The Cu/Fe ratio
in the loaded and scrubbed organic solution can meet the industrial requirement and
prevent excessive amounts of iron transfer to the electrowinning circuit.

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Acknowledgements
The authors would like to thank Falconbridge Limited (now Glencore) for funding
this project and allowing for publication and also thank BASF for supplying the solvents

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and advice on experimental methods.

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References

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Demarthe, J. M., Gandon, L., Georgeaux, A., 1976. A new hydrometallurgy process for
copper, In: Yannopoulos, J. C. and Agarwal J. C. (Eds.), Extractive Metallurgy of

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Copper, TMS, AIME, New York, 825-848.
Dutrizac, J.E., 1992. The Leaching of sulfide minerals in chloride media,
MA
Hydrometallurgy, 29, 1-45.
Hyvarinen, O., Hamalainen, M., 2005. HydroCopperTM a new technology producing
copper directly from concentrate, Hydrometallurgy, 77, 61-65.
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Liddicoat J., Dreisinger, D., 2007. Chloride leaching for chalcopyrite, Hydrometallurgy,
TE

89, 323-331.
Lu, J., Dreisinger, D., 2013a, Copper chloride leaching from chalcopyrite concentrate,
P

Minerals Engineering, 45, 185-180.

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Lu, J., Dreisinger, D., 2013b, Copper chloride leaching from chalcopyrite and bornite
concentrates containing high levels of impurities and minor elements,
AC

Hydrometallurgy, 138, 40-47.

Lu, J., Dreisinger, D., 2013c, Solvent extraction of copper from chloride solution I
extraction isotherm, Hydrometallurgy, 137, 13-17.
Lu, J., Dreisinger, D., 2013d, Solvent Extraction of Copper from Chloride Solution II:
Cuprous Oxidation by Oxygen Coupled with Simultaneous Cupric Solvent
Extraction, Hydrometallurgy, 138, 48-53.

Moyes, J., Houllis, F., Bhappu, R.R., 2000. The Intec copper process demonstration
plant. 5th Annual Copper Hydromet Roundtable'99 International Conference;
Phoenix, AZ; USA; 10 Oct. 1999. Randol International, pp. 6572.
Muir, D. M., Senanayake, G., 1984. Refining of CLEAR copper powders by the Parker

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Process. A comparison of the chemistry of copper impurities in chloride and sulphate

media. Proc. Symposium on Extraction Metallurgy, Aus.I.M.M., Melbourne, pp. 353-
359.
Peters, E., 1977. Applications of chloride hydrometallurgy to treatment of sulfide

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minerals, In: Chloride Hydrometallurgy, Brussels, Benelux Metallurgie, 1-36.
Virnig, M., Fisher, G. M., 2003. Solvent extraction process for metal recovery, US

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Patent 6599414.

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Winand, R., 1991. Chloride hydrometallurgy, Hydrometallurgy, 27, 1991, 285-316.

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Highlights

Two-stage countercurrent copper SX from cuprous chloride was conducted.

In Stage 1, Cu-loaded organic phase was pre-scrubbed using CuCl and FeCl2 solution.
In Stage 2, Cu was loaded to organic phase by Cu(II) SX coupled with Cu(I) oxidation.
Fe was removed to a satisfactory level by scrubbing using CuSO 4 and H2SO4 solution.
Two-stage Cu SX was feasible to transfer Cu from chloride to sulfate solution.

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