COMBINED ION EXCHANGE - SOLVENT EXTRACTION

PROCESS FOR COPPER RECOVERY

Georgi Savov , Todor Angelov, Valeri Tsekov
Iontech Engineering Ltd., Sofia, Bulgaria
Ivan Nishkov
University of Mining and Geology "St.Ivan Rilski", Mineral Processing and Recycling
Department, Sofia, Bulgaria
Nikolajcho Nikolov, Gerasim Konzulov
Bucim DOOEL, Radovis, Macedonia
Abstract: The combined process developed using Ion Exchange, Solvent Extraction and ElectroWinning (IX-SXEW), is described. This method is excellent for processing of pregnant leach solutions both from spent and new
copper heaps and dumps, acid mine drainage and other industrial streams. The process produces high grade,
marketable cathode copper. The effluents produced from the process totally meet stringent environmental
standards. The Buchim Copper Project in Macedonia for heap and dump leaching and copper recovery unit
operations of the proposed flow sheet is described. Key findings of the process and comparison between
conventional SX-EW process and novel process are also presented.

Key Words: Hydrometallurgy, Copper recovery, Leaching, Ion exchange, Solvent extraction, Electrowinning
1.

INTRODUCTION

The IONTECH L/IX/SX/EW process is very

promising in the recovery of copper from different
chemical solutions.

It shows clearly that the IX process can be

successfully included in the L/SX/EW scheme. As
the name suggests the method involves four major
stages:
1.1.

Leaching

The process by which copper ions are removed

from the ore using chemical agents called lixiviants,
mostly sulfuric acid solution. When lixiviant
solution is applied to the ore, it dissolves the
present copper ions to produce a Pregnant Leach
Solution (PLS).
1.2.

Picture 1. Copper recovery using IONTECH L-IXSX-EW Process

Picture 1. depicts the overall process whereas Lleaching, IX-ionexchange, SX-solvent extraction,
EW electrowinning, O-ore, W-spent ore, PLSpregnant leach solution, F-filtrate, LR-loaded
resin, SR-regenerated resin, RF-raffinate, RSregenerate, LO-loaded organic, SO-stripped
organic, PE-pregnant electrolyte, SE-spent
electrolyte, C-charging, R-regeneration, Eextraction, S-stripping.

Ion Exchange

In this process the copper containing PLS is passed

through the resin laid in the columns and copper is
adsorbed on the resin. The column is then
regenerated with sulfuric acid solution to obtain
highly purified copper electrolyte, suitable for the
further treatment through solvent extraction
process.
1.3.

Solvent Extraction

In SX process an organic extractant that binds

copper but not impurity metals is dissolved in an
organic solvent (diluent) and is mixed with the
copper containing aqueous solution. The copperloaded organic solution is separated from the
aqueous solution in a settler tank. The barren
aqueous solution, called raffinate is sent back to the

leaching-ion exchange process. Sulfuric acid

solution, mostly spent electrolyte returned from the
EW process is then added to the loaded organic
mixture, which strips the copper into an electrolytic
solution ready for electrowinning.
1.4.

Electrowinning

Electrolysis of a pregnant electrolyte solution,

produced in SX process, such that copper ions
within it are plated onto the cathode.
2.

PROCESS DEVELOPMENT

Metal recovery by Solvent Extraction (SX) process

is a well-known technique that is practiced
commercially for the recovery of copper, uranium,
nickel, cobalt, molybdenum and other metals.
Copper SX has been used for approximately 40
years. Despite the wide acceptance of SX, it does
have some shortcomings that have several negative
impacts. SX employs large quantities of volatile
organic substances. SX extractants are potential
toxins and certainly pose an environmental concern.
Crud generation, which is fact of life in SX
process requires special facilities and causes
economic losses and downtimes. The organic losses
resulting from the liquid organic phase are an
environmental hazard to ground water and lead to
economic losses and EW operating problems.
Solvent extraction is very sensitive to low
temperatures. This causes bad phase disengagement
times and therefore poor process performance.
The combined L/IX/SX/EW process using Ion
Exchange and Solvent Extraction, developed by
IONTECH, offers a method, which overcomes SX
negative characteristics shown above.
The key findings of the process are:
(1) The process is suitable for recovery of copper
from PLS with metal concentrations, varying on a
broad range as well as for treatment of solutions in
the decommissioning of spent copper dumps, acid
mine drainage /AMD/ and ammonia etch solutions;
(2) Can be operating effectively with very lowgraded copper pregnant leach solutions thus results
in prolonged projects life, compare to solvent
extraction recovery only;
(3) The construction of large ponds for pre-filtration
of the PLS is not necessary. In this case, very
sensitive solvent extraction process can be work
properly even at intensive rainfalls and with turbid
solutions and solutions containing large quantities
of suspended solids;
(4) Winter operation without troubles. SX can be
work properly i.e. with good phase disengagement
times, even at low temperatures. This is due to high
temperatures of IX regenerate used as a SX feed;
(5) Combining of ion exchange and solvent
extraction strongly reduces organic losses and crud
formation;

(6) Integration of the IX process in SXEW scheme

can be used for control of metal/acid ratio as well as
Cu/Fe ratio, which are very important for SX
process;
(7) Combining of ion exchange and solvent
extraction reduces EW organic problems and thence
improved copper cathodes quality;
(8) Ion Exchange - Solvent Extraction Electrowinning technological approach lead to SX
plant sizes reducing. Thus, minimizes the floor
space requirements for SX footprint ;
(9) The IX-SX combination is characterized with
similar capital cost and lower operating cost
compare to solvent extraction process only.
3.

BUCHIM COPPER PROJECT

3.1.

General Description

The Buchim Copper Project, scheduled for

construction and operation in 2011 is a treatment
plant at the Buchim mine site in Macedonia. The
Plant has been designed to treat the pregnant leach
solutions from the existing Old Dumps via Iontech
L/IX/SX/EW process and recover copper into high
grade copper cathodes. An oxide heap leaching will
be set into operation later. The Iontech technology
was selected as the best available technology for the
site not only due to the fact that the final product is
with extremely high quality, but also due to its
ability to achieve the stringent environmental
demands.
Buchim copper mine is situated near the village of
Buchim and in the south borders of Plachkovitsa
Mountain, in Republic of Macedonia. Dominating
top in the immediate surrounding is Versnik, on 720
meters above the sea level, while 620 meters is the
average above the sea altitude of the ore deposit.
Buchim mine territorially and administratively
belongs to the municipality of Radovis. It is 95
kilometers away from the Skopje capital, and 170
kilometers from the nearest port Thessaloniki
(Republic of Greece).
3.2.

Facility Operation Design

The Buchim Copper Project includes the following

operation: the Leaching and Ion Exchange
Solvent Extraction Electrowining (L/IX/SX/EW)
facilities. The main structures at the new designed
mine complex are the old dump, new constructed
oxide heap, main pump station, leaching circulation
piping, two raffinate ponds and a controlemergency pond; IX/SX/EW plant and support
facilities.
Facility Map Location is shown on Pictures 2,
where: 1-Old Dump; 2-New oxide ore Heap; 3-IXSX-EW plant; 4-first PLS pond; 5-second PLS
pond; 6- Control-emergency pond; 7-leekage
collecting barrage; 8-pre settling mini pond.

Picture 2. Facility Map Location.

(1) Dump and Heap Leaching Operations.
The leach dump covers approximately 550 decares.
The total height of the dump (in the southern part)
is approximately 100 m. Copper tenor in dumped
ore ranges 0.12 0.15 %. Main minerals are
limonite, cuprite, tenorite, native copper, goethite,
malachite, azurite, but relicts from pyrite,
chalcopyrite, chalcocite,
specularite,
rutile,
magnetite, etc also occurs.
The leach heap is newly designed over previously
covered by HDPE liner naturally formed valley. It
is designed to take about 6 millions tones oxide ore
and is disposed on 120 decares. It is projected to
mine and leach each year of about 1 million tones
ore. Copper tenor in oxide ore ranges 0.15 0.35
%. Main minerals are mostly the same as in the
dump, with slightly advantage in favor of oxidized
species.
In the leaching operation a sulfuric acid solution is
applied to the surface of the dump at rates of twelve
litres per square meter each hour. Pregnant leach
solution (PLS) forms as the acid solution percolates
through the pile and dissolves copper minerals into
the aqueous solution as copper sulphate. The PLS
flows down through the entire dump until it reaches
the drainage layer where it enters the collection
PLS pond. The resultant solution containing about
0.5 grams per liter of copper is suitable for
purification and concentration by the ion exchange
and solvent extraction processes. The piping
network for the dump comprises HDPE main lines
at ground level and supply header pipes along the
dump, which distribute solution over the surface
through a series of dripper lines.

(2) Ion Exchange Operations.

The IONTECH process involves treatment of the
PLS stream from dump leaching with the ion
exchange facility for copper removal, and the
subsequent recovery of the copper as a high purity
cathode product by solvent extraction and
electrowinning. Feed solution pH ranges from 1.8
to 2.2, with a design feed flow rate of maximum
650 m3/h. The facility consists of 8 ionexchange
columns - 4 IONTIX units (IONTECH Design).
Copper concentration in the feed is not less than 0,5
g/l and the copper concentration in the discharge
effluent averages 0,02 g/l. Elution of each column
with a sulfuric acid solution (160-200 g/l H2SO4)
produces an upgraded loaded electrolyte solution of
15-18 grams/liter copper. High purity copper
cathode is then produced from this solution by
solvent extraction and electrowinning.
(3) Solvent Extraction/Electrowinning Operations.
The Solvent Extraction/Electrowinning plant
(SX/EW) consists of the plant feed pond, the
raffinate pond and the SX/EW plant. From the PLS
pond solutions are directed to IX facility and next
the obtained IX regenerant is pumped to plant feed
pond, where it is mixed with pregnant leach
solution from the leach operation.
Feed solution from the plant feed pond flows into
the solvent extraction plant (SX) at a rate of
30m3/h. The SX plant has 1 train, with three
extraction and two stripping stages. In the
extraction stage, the feed solution is thoroughly
mixed for a few minutes with an organic liquid
which consists of extractant and diluent and having
a strong attraction for copper ions. The extractant
formed an organic complex with the metal ions and
copper transfers from the aqueous to the organic
phase. After mixing, the organic and aqueous
solutions separate in the settler, since they are
immiscible. The copper loaded organic then flows
over weirs into a loaded organic (LO) tank which is
equipped with coalescers. Not all copper has been
removed from the partially stripped aqueous
solution, so it is routed to a second and third
extraction stage to be mixed again with barren
organic. The loaded organic from the third
extraction stage is sent back to the first stage as to
collect copper from the richer feed solutions.
In the stripping stages, a spent electrolyte from the
electrowinning plant is contacted with the loaded
organic coming from the LO tank. During this
contact the electrolyte stripping the copper of the
organic. Copper binds to the electrolyte, and the
final pregnant electrolyte (PE) is drawn from an
aqueous weir and flows by gravity to the electrolyte
feed tank. After filtration, the strong electrolyte is
transferred to the electrowinning operation for final
recovery of copper.
Once stripped of copper in the extraction tanks, the
barren aqueous solution (raffinate) from the solvent
extraction tanks is routed by gravity to the raffinate

pond where solution is recycled to the leaching

operation.
The electrowinning operation at the plant has a total
production capacity of 2800 tons per year. The
electrowinning operation consists of rectifiers that
provide an output capacity of 13 000 amperes and
50 volts that are distributed to the cells. The EW
facility contains 24 cells in total, with each cell
constructed of polymer concrete. Twenty six lead
anodes and twenty five stainless steel mother blank
cathodes are placed in each cell. The cathodes are
on a 10 cm spacing .The current is distributed to the
cells and flows through the electrolyte to the
cathode. Copper is plated onto stainless steel plates
to obtain concentrate that is 99.999% copper.
(3) Copper Cathodes
The cathodes remain in the cell for up to 7 days,
before they are taken from the cells by an overhead
crane. The crane takes several cathodes to a wash
pool, where remaining electrolyte is washed off.
The copper deposition is removed by hand using a
hammer and chisel. The cathodes blanks are then
rinsed and returned to the cells.
3.3.

Engineering of the project

Engineering of the project, the technical process of

transforming a business opportunity into an
industrial plant, includes the following phases:
(1)Scoping Study- includes base evaluation of the
optional process schemes and costs;
(2)Feasibility Study- includes process details as
well as detailed estimation of capital and operating
costs;
(3)Financial Analysis - determination of the most
cost effective financing packages;
(4)Metallurgical Test work includes evaluation
of the ore samples, construction materials
determination and most important recovery
procedures identification;
(5)Design, Supply and Construction - includes
optimization the process and equipment, design,
supply and construction of the plant;
(6)Commissioning and Start-up - includes
training for the plant operation team as well as
technical and operational support

4.

CONCLUSIONS

This paper has briefly described the application and

key findings of a novel hydrometallurgical process,
which uses combination of Leaching, Ion
Exchange, Solvent Extraction and Electrowinning
for the recovery of copper from the Buchim area
ores.
The process described is simple, energy efficient,
environmentally friendly and with high recovery
efficiency of the copper. It was applied company
proven equipment and facility disposition.
The project design decided operational management
of leaching solutions, mine water drainage coming
from old dump and other contaminated water in the
area.
Project is designed environmentally friendly and
with proven economical effect for copper recovery
both from old dump and new mined oxide copper
ore which is unsuitable for conventional flotation
treatment.
LITERATURE
[1] RfP 21/2008, Feasibility assessment and
Development of a main technical design for water
protection measure Buchim mine, Radovish
municipality, FYR Macedonia.
[2] Bartlett, R.: Leaching an Fluid Recovery of
Materials, Second Edition, 1992
[3] Jergensen V.G.: Copper Leaching, Solvent
Extraction and Electrowinning Technology, SME,
1999.