The Development of the Escondida Leach Process and its

Implementation in the Escondida Copper Cathode Plant

Willem P C Duyvesteyn 1

ABSTRACT
BHP is the world's largest copper concentrate producer with production
from mines at Escondida (Chile), Ok Tedi (Papua New Guinea), and
Island Copper (Canada). The entire concentrate production is further
processed into refined copper by third-party smelters around the world. In
anticipation of an expansion in the global copper concentrate production
capacity and a corresponding increase in treatment and refining charges
80 :., ':: .
by copper smelters, BHP has continuously evaluated various
opportunities for downstream copper processing. An expansion in the ~u$ ~->
Escondida mine production, combined with BHP's interest in processing
some of its concentrate production on-shore in Chile, ultimately resulted
in the development of the Escondida Leach Process. This process was c I
specifically developed for higher grade concentrates, such as from o 60 . II
';;
Escondida. :2 i
'0
An ammoniacal lix.iviant and air are used under ambient conditions to
leach less than one-half of the contained copper values. After solid-liquid en
en I
I
separation, the solution is subjected to solvent extraction regenerating the
ammoniacal lixiviant and the copper loaded organic phase is stripped in
spent electrolyte returned from the electrowinning plant where ultra-high
C
.
Cl)
Q.
40 .... .
0-
.
\.r-r:
.
:j
quality SX-EW copper is produced. The solid leach residue can, if Q.
required, be upgraded by flotation to produce a high-grade copper o
concentrate with improved fuel values and a pyrite tail for disposal. (J Ii
After an 18-month bench and pilot plant scale program and an
engineering feasibility study, Minera Escondida Limitada decided to build 20 ....
an 80 000 tonnes of copper per year facility near Antofagasta, Chile. The j
installed investment cost amounted to around $160 million. The plant
went into commercial production in November 1994 and better than I
99.9995 per cent Cu cathodes were produced right from the start.
BHP believes that the process and the commercial plant are an
excellent example of a novel approach advancing the science of copper
metallurgy in harmony with present demands for environmentally sound
processes and high quality products. 1 10 100

INTRODUCTION Leaching Time - minutes

Initial test work on the Escondida process started in early 1990 by

Duyvesteyn and Sabacky (1993) at BHP Minerals' Laboratory in
Sunnyvale, California. While investigating the removal of the
adsorbed ferrocyanide complexes from the surface of copper
minerals with sulphuric acid, Escondida copper concentrates
were shown to be readily soluble in an acid environment. BHP
Minerals' Laboratory continued to explore acid leaching of
Escondida concentrates as an alternative to smelting. Although
total dissolution was attempted, mineralogical investigations at
TML showed that just a partial leaching would result in complete
liberation of gangue and pyrite components from copper minerals
in concentrate middling particles.
Extremely fast initial leaching rates under mildly-oxidising
conditions were also observed. However, after about one hour of
leaching, a significant reduction in copper dissolution rate
occurred. This was earlier established by Mao and Peters (1982)
and is illustrated in Figure 1.
Further investigations confirmed that the initial fast reaction
rate was due to oxidation of monovalent copper and that the
much slower secondary reaction was due to oxidation of sulphide
sulphur. Because of these early findings, the earlier version of
the Escondida process combined fast initial sulphuric acid
leaching for partial copper dissolution with a residue flotation
I. Manager Minerals Technology, BHP Minerals,
204 Edison Way, Reno, Nevada 89502, USA.
FIG I - Acid leaching of chalcocite.
upgrading step to produce a final concentrate with chemical
specifications similar to the feed. Since over 30 SX-EW plants
have been built since the pioneering days at Nchanga and because
the SX-EW product is now widely recognised as a superior
copper product, the use of solvent extraction and electrowinning
to produce a premium cathode product from a copper concentrate
was deemed essential for commercial success of the process.
With a further definition of the process, the disadvantages of
integrating solvent extraction with an acid leaching system
containing high copper concentrations were apparent. Low acid
levels in the raffinate stream would be inadequate for recycle to
concentrate leaching. As solvent loading can be significantly
higher from ammoniacal solution than from acid systems, and
since high concentrations of ammonia in raffinate would be
available for recycle to leaching, developmental work was
redirected toward the use of an ammoniacal lixiviant. Further
benefits of ammonia were identified:
1. A full-strength lixiviant can be generated for recycle to the
leaching step, requiring very little make-up ammonia.
2. Milder leaching conditions are employed. Use of air for
oxidation at ambient temperatures is feasible and
atmospheric pressure results in lower costs for capital
equipment.

World's Best Practice in Mining and Processing Conference Sydney, 17 - 18 May 1995 29
 WILLEM P C DUYVESTEYN

3. Essentially no impurity elements are solubilised. Around 49r--------------......,

50 per cent of the copper, and only minute quantities of
nickel, cobalt, zinc, and silver will go into solutions as they
can form ammoniacal complexes. . ... "." .... ":

4. The SX section of an ammonia plant could be significantly

smaller than an equivalent acid one.
;::, 45
5. A lower strength sulphuric acid can be used for stripping o
providing further opportunities for a high quality copper
product as lead contamination can be minimised.
'#. ,. .
., :Column..
'43
As described by Kuhn (1974), the Arbiter process is an G) ,.,.
Cleaning
ammonia-based process which was developed in the 1970s to
compete head-on with replacing copper smelting. As such it had
.. 41
't'
ca
C'
.
. ..
' \:
,," ':.
.
'

to compete with the high copper recoveries (97 per cent) that are
generally experienced. This required rather aggressive leaching
...ca
G)
M"'chanical .:. , . \ ~

conditions as shown in Table 1. ~

G)
39 ~eU . CI~ani.i)g ~.~ ~

1
TABLE
u \
c \
Comparison ofthe Escondida and Arbiter processes. o
037 . \

Item Escondida Process Arbiter Process

\ :
\:
Feed mineralogy chalcocite and bornite any copper mineral
35
.. ,
..'. ~'.' . \:.
Leaching time one hour eight hours
Leaching temperature ambient near boiling ~

Copper dissolution less than 50% over 90% 33'-------------------'

Sulphur oxidation less than 2% over 90% 82 83 84 85 86 87 88 89 90
Precious metal recovery by residue flotation none or residue leaching
Oxygen source air tonnage oxygen Copper Recovery - %
Cathode quality very high average
Sulphur disposal none needed gypsum or (NH4)2S04 FIG 2 - Upgrading of Escondida concentrate.
(Pilot Plant data 1984).

Completion of bench-scale work followed by a successful mini TABLE 2

pilot plant run using the ammonia circuit led to construction and
operation of a 600 kg concentrate per day leach-solvent Copper to sulphur ratios for various concentrates.
extraction-electrowinning pilot plant. The construction of the Concentrate CODDer Iron Sulphur SICu ratio
plant was completed in June of 1991 and it operated around the
clock five days per week until the end of November 1991. An Escondida 41 16 28 0,68
existing pilot flotation plant was used to study the upgrading of Morenci 24 26 36 1.50
leach residues to original concentrate grade. Kennecott 29 25 31 1.07
Mtlsa 24 29 32 1.33
ALTERNATIVES TO THE ESCONDIDA PROCESS Hitachi 26 25 30 1.15
During the 1960s, 70s and early-80s a variety of
hydrometallurgical processes (Cymet, CLEAR, USBM,
DuPont-Kennecott, Arbiter, Sherritt-Cominco, etc) were Soon after the start-up of the Escondida project in 1990, the
developed to overcome the problems perceived to exist with outlook of the copper market changed from an oversupply to
smelting and refining of copper concentrates. S02 pollution was shortage and metal prices improved. As a result, plans were put
thought to be the main culprit that ultimately could be responsible into place to expand the plant from about 320 000 tpa of
contained copper to over 400 000 tonnes. Even demand for metal
for the demise of the copper smelting industry. Now in the 1990s,
improved, no additional smelting capacity was under construction
a large number of pyrometallurgical processing routes have been and it was believed that having access to some downstream
installed on a commercial scale and copper smelting continues to capacity could balance a projected surge in smelter treatment and
be the work horse of copper processing. Following the shutdown refining charges. It was also believed that building a downstream
of the CLEAR Process commercial plant, few hydrometallurgical processing facility in Chile would not only represent good
processes for treatment of copper concentrate remain in corporate citizenship but sound business practise as well. Several
commercial practise. studies were carried out during the 1980s which all showed that
The Escondida process was not developed as an alternative to building new copper smelting capacity in Chile would be
copper smelting, but rather as a complement to smelting and marginal at best, even assuming attractive treatment charges. The
refining. Before the start-up of the Escondida mine and mill, main problem was related to the capital intensive nature of
bench-scale flotation testwork had suggested the ore responded greenfield copper smelting requiring around US$40OO per annual
well to upgrading, especially by column cells rather than pound of copper treatment capacity. All the studies indicated that,
mechanical cells. This upgrading potential is shown in Figure 2. although Escondida concentrates are considered a premium
This resulted in Escondida being one of the first new copper concentrate by custom smelters, these advantages could not be
mills to be built and equipped with column cleaning only. One translated into substantially lower capital and operating costs for
disadvantage of processing high-grade chalcocite concentrate in a dedicated Escondida smelter project.
copper smelters is the rather low copper to sulphur ratio, which Furthermore, if a smelting project were to be economic, the
sometimes could require the use of additional fuel for smelting. unit would have to be so large that either the mine had to be
A comparison between Escondida and other concentrates expanded more than could be justified at that time or that the
showing a significant sulphur shortage is given in Table 2. existing long-term concentrate supply contracts with customers

30 Sydney, 1718 May 1995 World's Best Practice in Mining and Processing Conference
 THE DEVELOPMENT OF THE ESCONDIDA LEACH PROCESS

who depended upon the continued supply of high quality where R represents the active ingredient of the organic phase. In
concentrates would be jeopardised. Escondida obviously wanted the extraction reaction, the copper amine complex is broken,
to maintain the excellent relationship it had with its customers. liberating ammonia in the raffinate for recycle to the concentrate
Therefore, the question raised was how can Escondida satisfy leaching step. The stripping of copper from the organic phase is
all these needs: a smaller processing facility that takes full benefit shown in the following equation:
of the high quality of the concentrates and improvements in
minor disadvantages associated with a high quality concentrate CUR2(org) + 2H+(aq) ~ CU++(aq) + 2HR(org) (4)
(too little sulphur, too much copper). This resulted in the
development of the Escondida process. Copper is finally recovered as cathode copper via conventional
electrowinning. An Escondida process flow sheet is shown in
THE ESCONDIDA PROCESS Figure 3. This flow sheet depicts a general implementation of the
process as has been installed at Coloso, Chile by Minera
The Escondida process produces high-quality cathode copper and Escondida Limitada.
high-grade copper concentrates for smelting through a novel
hydrometallurgical treatment of monovalent copper containing A novel approach to copper hydrometallurgy
concentrates. In simple terms, the process can be represented by
the following equation: Duyvesteyn and Hickman (1993) invented the Escondida process
where the best components of conventional copper
hydrometallurgy are combined (leaching, solvent extraction and
CU2S ~ Cu + CuS (I) electrowinning). Some novel features of the process include the
chalcocite copper covellite
following:
The incoming copper concentrate stream ('chalcocite') is split I. The partial dissolution of monovalent copper, yielding
into two high quality products: high quality cathodes ('copper') copper in solution and also an upgradeable residue, avoids
and an upgraded sulphide concentrate ('covellite'). Obviously, the troublesome removal of sulphur oxidation products
the process is more complex than depicted by the above equation. (ammonium sulphate or gypsum). Rates for partial
The process is amenable to a variety of copper concentrates, but dissolution are an order of magnitude faster than rates for
the highest efficiencies are obtained with concentrates containing total dissolution.
a predominance of monovalent copper containing minerals. 2. The use of an ammonia-ammonium sulphate lixiviant to
Table 3 shows the degree to which the commercially important form the cupric ammonium sulphate complex yields high
copper minerals respond to leaching conditions present in the copper concentrations in solution and therefore smaller
Escondida process. liquid/solid separation and solvent extraction equipment are
required.
TABLE 3
Composition ofcopper minerals. 3. The ammonia-ammonium sulphate leaching environment
brings few impurities into solution. Only copper, and to a
much lesser extent nickel, cobalt and zinc are solubilised.
Mineral Chemical Alternative Monovalent Projected Solvent extraction is actually more a lixiviant regeneration
Fonnula Fonnula Copper Copper system than a purification operation. Ammonia is recovered
Content Dissolution and copper is transferred to the acidic sulphate environment
Chalcocite CU2S CU2S 100% 50% for eleetrowinning.
Bomite CusFeS4 2CU2SCuS-FeS 80% 40%
4. As a very pure copper sulphate solution is generated for
Digenite CUl.8S 3CU2S-2CuS 75% 37.5% electrowinning, the highest quality cathode copper is being
Chalcopyrite CuFeS2 CU2S-2CuS-3Fe 50% 25% produced by the Escondida process. Because a lower free
S-FeS2 acid concentration is adequate to strip copper from the
Covellite CuS CuS 0% 0% organic extractant, lower anode corrosion rates (lower lead
contamination) and lower sulphate incorporation in cathode
copper has been experienced.
In detailed terms, chalcocite or similar minerals react with
5. The process can compete with eXIStIng smelting
atmospheric oxygen in an ammonia-ammonium sulphate solution
technologies, as it will produce the highest possible cathode
to produce copper amine sulphate and covellite as a leach residue.
product quality, with few environmental limitations and
The overall leaching reaction is shown below:
with lower capital and similar operating costs.
Cu2S + 2NH3(aq) + 2NH/(aq) + 02 ~ CuS + 6. As the Escondida mill can produce high-grade concentrates,
Cu(NH3)4++ + H20 (2) occasionally customers might object to this grade and the
rather low corresponding sulphur content and fuel value.
This equation shows that the reaction requires both free ammonia Removing part of the copper and upgrading the
and ammonium ions. Leach residue, consisting of covellite, other sulphur/copper ratio has been beneficial in certain
minor copper sulphides, as well as pyritic and silicate gangue circumstances.
minerals, is separated from the leach solution, washed, and
upgraded by flotation (rejection of silicates and some pyrite to Ammoniacal leaching - fundamentals
tailings) to produce a final concentrate of equal or higher grade
than the original material. The chemistry of copper sulphide oxidation in the
ammonia-ammonium ulphate system is complex and is
Copper in the leach solution is recovered using a solvent influenced by many variables including temperature, oxidant
extraction-electrowinning process. Copper is extracted into the concentration, ammonia and ammonium salt concentration, and
organic phase according to: the formation of a series of copper amine complexes. Leaching is
possible through stabilisation of the cupric ion in solution as the
Cu(NH3)4++ (aq) + 2HR(org) ~ CUR2(org) + 2NH3(aq) + tetra-amine complex. According to Tozawa et al (1976) the
2NH4+(aq) (3) following equilibria determine the region of stability of the
complex:

Wol1d's Best Practice in Mining and Processing Conference Sydney, 1718 May 1995 31
 WILLEM P C DUYVESTEYN

MILL COPPER CONCENTRATE

MAKE-UP
AMMONIA
FILTER CAKE

B LEED
1 I FILTRATE
FILTRATION

AIR
LEACHING
WATER
WASH TREATMENT
WATE R TO
DISPO SAL

LIQUID-SOLID RESIDUE
RAF FINATE SEPARATION FLOTATION
RESIDUE
SOLUTION

TAILI NGS
WASH WATER
SOLVENT FINAL COPPER
EXTRACTION CONCENTRATE
ELEC TRICAL
ENER GY
I
PREGNANT SPENT BLEED

ELECTROWINNING I

COPPER CATHODES
1
FIG 3 - Flow sheet of the Escondida process.

(5)

.I~_N;;.:H~.::.I++IN~H:;.;:.::.I_-...:;m~O;.;I:..:.II C...:UI_NH...:.::..:.I;_m_ol_II__>_71._O_IO._1---;O~.O,l
(6) 2.0 ....
\ I
\ I
\ I
(7) \
I
I
1.6 " I

,,
\
I
Tozawa combined the equilibrium constants for these reactions \

,,
\
and obtained a relationship between pH, total ammonia \

concentration and copper concentration and regions of stability 1.0

\
\ ,
for the cupric amine complex as a function of pH and ammonia
\
,, ,,
activity can be delineated as shown in Figure 4. "" ...
#,;",
To achieve high total ammo~ concentrations and to maintain 0.6 .... _---- CuO.
solution pH in the Cu(NH3)4 +-stable region, the system is
buffered with ammonium sulphate. High copper tenors are thus CuO. .. ,
achieved in the region of complex stability. The dissolution of 0.0
copper-containing sulphides has been studied by several 7 8 9 10 11 12
investigators (Majima and Peters, 1966, and Peters, 1976). As pH
with copper metal, the oxidation and dissolution of chalcocite is
believed to proceed through the formation of the
Cu(NH3h+-complex which is rapidly converted to the
FIG 4 - Cu(NH3)i+ complex stability as a function of ph
CU(NH3)42+-complex via reaction with dissolved oxygen. The
and ammonia activity.
dissolution of chalcocite can, therefore, be represented by the
following two steps:,
As stated previously, the overall leaching reaction in
ammoniacal solution becomes:

32 Sydney, 17 - 18 May 1995 Wor1d's Best Practice in Mining and Processing Conference

Stanczyk and Rampacek (1966) studied the dissolution of
various copper sulphides using ammoniacal solutions and showed
that final copper recovery was very low when no ammonium
sulphate was used.
Kuhn et al (1974) also investigated the dissolution of copper
sulphide minerals in ammonia-ammonium sulphate solutions. To
achieve nearly complete dissolution of copper, an intensive
mixing regime was employed for adequate oxygen mass transfer
through the bulk solution to the mineral surface.
Ek et al (1982) also studied the ammoniacal leaching of copper
sulphides at different temperatures and different 02 and NH3
partial pressures. According to their results, only 50 per cent of
copper contained in chalcocite and bornite can be solubilised
under optimum leaching conditions. They observed that addition
of ammonium sulphate to the leach solution eliminated the
build-up of the oxidised phase around the particle, thus
reinforcing the need to use a sulphate-buffered system to
maintain complex stability in high copper content leach solutions.
Based on these investigations, one can postulate that the
conversion of chalcocite and similar minerals to covellite in
oxygenated ammoniacal solutions proceeds in the following
sequence of reaction steps:
1. Dissolution of gaseous oxygen in the solution at the
gas-liquid interface.
2. Oxygen mass transfer through the bullc leach solution to the
particle surface. This step is dependent on the oxygen
partial pressure and the mixing regime.
3. Adsorption of oxygen on the mineral surface.
pyrite
cathode
Flo 5 - Galvanic leaching of chalcocite.
World's Best Practice in Mining and Processing Conference
THE DEVELOPMENT OF THE ESCONDlDA LEACH PROCESS
4. Galvanic leaching occurs when one mineral (pyrite) is in
contact with another one (chalcocite), as proposed by Peters
et al (1972). A potential is created which accelerates the
anodic dissolution of chalcocite. A galvanic current flows
and electrons are given up by copper to produce copper
ions. Electron are accepted by the oxygen adsorbed on the
pyrite surface, causing a cathodic discharge and producing
OH- ions according to:
(11)
The phenomenon of chalcocite becoming a sacrificial anode
will be accentuated in pyrite-chalcocite middling particles
where there is an intimate contact between anode and
cathode.
5. Since covellite has a smaller molar volume than chalcocite,
shrinkage occurs and pores are created providing the means
to transport the chemical reaction products. This will
ultimately result in the chemical 'comminution' of the
middling particles and in the generation of liberated copper
sulphide particles (covellite). The presence of a strong
complexing ligand (NH3) leads to desorption of Cu 2+-ions
from the sulphide surface, forming a soluble copper amine
complex. Initially the cuprous complex is formed, which
will be oxidised by oxygen into the cupric one. See
Figure 5. The transformation of chalcocite to covellite
proceeds through several more or less stable intermediate
phases, such as CUl.96S (djurleite), CU1.8S (digenite), CU1.7S
(anilite), and CUl.lS (blaubleibender covellite).
6. Diffusion of the cupric amine complex into the bulk
solution.
shrinkage pores
anode
Sydney, 17 - 18 May 1995 33
WILLEM P C DUYVESTEYN
Ammoniacal leaching results of laboratory
investigations
For laboratory investigation of the ammoniacal leaching system,
a conventional flotation cell was used as a leach reactor.
The more important variables that were investigated for the
ammonia-ammonium sulphate leaching system were:
oxygen mass transfer (different leach reactors);
free ammonia concentration (25 to 100 gpl);
ammonium sulphate concentration (40-150 gpl);
particle size (-lOO +200 mesh, -200 +400 mesh, and -400
mesh);
temperature (22C to 66C).
The influence of oxygen mass transfer
Figure 6 shows copper extraction results for three different
methods of oxygen introduction into the leaching system. In one
case, air was entrained in the leach solution via the vortex
generated by a simple, four-blade mixing impeller. In the next
case, an air distributor was used with the impeller and in the third
case, a flotation cell was used as the leach reactor. The difference
in copper extraction rate when leaching with a four-blade
impeller with an air distributor and when leaching with the
flotation cell demonstrates the much improved oxygen mass
transfer achieved with the latter device.
Copper Extraction - %
50,..------------------------,
40
30
34 Sydney, 17 - 18 May 1995
The effect of free ammonia concentration
Leaching experiments were performed at a temperature of 35C
with 250 gpl of solids and 80 gpl of ammonium sulphate and the
stoichiometric free ammonia concentration was adjusted to give
25 per cent, 50 per cent, and 100 per cent extraction of contained
copper in the concentrate feed. Figure 7 shows the dependence of
copper extraction on free ammonia concentration.
The effect of ammonium sulphate concentration
The effect of ammonium sulphate on copper extraction is
demonstrated in Figure 8. The experiments were carried out with
250 gpl solids, at 35C, and a stoichiometric amount of free
ammonia sufficient for 50 per cent copper extraction. The curves
show that at the higher ammonium sulphate levels (> 80 gpl) the
initial rate of copper dissolution is constant but that final
extraction is a function of applied ammonium sulphate
concentration. As expected, these results suggest that copper
dissolution is governed by the availability. of ammonium ions for
the formation of the tetra-amine complex.
The effect of total ammonia, [NH3 + NH4+l, on copper
dissolution rate was evaluated using copper extraction rates
derived from Figures 7 and 8. Extraction rates for the first five
minutes were ignored. Results are shown in Table 4.
The data in the above table show that the ratio of total
ammonia to total copper has to be around 2.5 to reach a
maximum extraction rate of 1.0 per cent Cu per minute. This
Flotation cell
0 Agitation with air
0 Agitation without air
World's Best Practice in Mining and Processing Conference

Copper Extraction - %
60 r - - - - - - - - - - - - - - - - - - - - - - - - . .
50
40
30
20 0 0
10
0
0
0
:)0
0 "
0 10 20 30 40 50 60 70 80
Leach Time - min
FIG 7 - Effect of free ammonia.
quantity of ammonia is somewhat more than what is necessary
for the Cu(NH3h+- complex. Adding more ammonia does not
further increase the extraction rate but it does increase the final
copper extraction as additional ammonia is needed to convert the
di-amine complex to the more stable tetra-amine complex.
The effect of initial particle size
To assess the effect of particle size of leach feed on copper
extraction rate, fresh concentrate was divided into three different
size fractions: -100 +200 mesh, -200 +400 mesh, and -400 mesh.
The copper content of the fractions was not uniform and ranged
from 28 per cent for the coarse to 45 per cent Cu for the fine
fraction. Free ammonia in the leach solutions was adjusted
for 50 per cent extraction and the [NH3 + NH/]ltotal copper
ratio was held constant. Results of experiments are presented in
Figure 9. As expected, the extraction rate is influenced by initial
particle size of the concentrate. Extraction rates were determined
to be: 0.47 per cent/min for the -lOO +200 mesh size fraction,
0.62 per cent/min for the -200 +400 mesh fraction, and 0.89 per
cent/min for the -400 mesh fraction.
The effect of temperature
Leaching experiments were performed at 22C, 42C, and 66C.
See Figure 10. The [NH3 + NH/]/Cu total molar ratio was held
constant. Under these conditions the temperature does not affect
the leaching rate significantly. This observation confirms findings
by other investigators that the first stage of chalcocite leaching is
controlled by a mass transfer step and not by a chemical reaction
World's Best Practice in Mining and Processing Conference Sydney, 17 -18 May 1995
THE DEVELOPMENT OF THE ESCONDIDA LEACH PROCESS
0
0 0 0
25 gpl NH 3
50 gpl NH 3
100 gpl NH 3
90 100 110 120
rate. As leaching at elevated temperatures may enhance the
conversion of sulphide sulphur to sulphate, process development
was focussed on operation at ambient to only slightly elevated
temperatures (40C). The operability of solvent extraction could
also be affected adversely by elevated feed solution temperatures.
Preparation for pilot plant leaching
To establish a benchmark for leaching performance, samples
were collected at Escondida through selective mining campaigns
to produce concentrate samples from a range of mineralised
zones in the Escondida orebody. Each of these concentrate types
was tested for copper extraction using standard laboratory
leaching procedures. The composition of pilot plant samples is
given in Table 5. Results for batch leaching of various pilot plant
samples are presented in Figure 11. Eight tests were performed
- two for each sample type. Results show that at least 40 per
cent of the copper in each sample can be extracted in a two-hour
leach.
Pilot plant campaigns
A 6oo-kg per day pilot plant consisting of leaching, solid/liquid
separation, solvent extraction and electrowinning was
constructed. Over a six-month period the following parameters
were tested in leaching: copper extraction, the effect of ammonia
concentration on copper extraction, and sulphur oxidation. In
addition to demonstration of process principles, critical
engineering data were gathered for commercial plant design,
including leaching times, oxidation air requirements, agitatior.
requirements, and 'best' ammonia addition strategy.
35
WILLEM P C DUYVESTEYN

served only to strip ammonia from solution. For Campaigns 4

TABLE4 through 12, oxidation air rates were lowered to near
Effect of total Ammonia [NH3 + NH4+ J on leaching rate. stoichiometric requirements for the first two leach vessels.
Excess oxidation air was used in the third vessel and no air was
[Nlll+NH/]/[Cul ratio Leachinl! Rate - % Co/min supplied to the fourth vessel. When ammonia concentrations were
1.70 0.425
maintained at sufficiently high levels in the leaching system, 40
per cent copper extractions were achieved with minimum air
2.25 0.525
requirements. The efficient utilisation of oxygen in the first vessel
2.54 0.960
needs to be mentioned. This may indicate that transfer of oxygen
3.31 0.975 through the air bubble-solution interface is not a rate determining
4.50 1.000 step in the overall oxidation reaction and that commercial-scale
leaching vessels can be designed with only marginal excess air
injection capacity.
Copper extraction
The effect of ammonia concentration
Copper extractions achieved in pilot plant operations are shown
in Table 6 and the extraction profile for a typical campaign is The most significant operating parameter affecting copper
shown in Figure 12. The copper extraction was calculated using extraction in the pilot plant leaching system was ammonia
the feed concentrate analysis, raffinate flow into the first leach concentration in the leach solution. What level of free ammonia
vessel, copper content of raffinate, volume of make-up ammonia, to maintain is shown in Figure 13.
and copper concentration of leach discharge solution. The The data shows a degree of scatter but a clear trend is apparent
make-up ammonia addition rate is also shown in Figure 12. - copper extractions up to about 40 per cent can be achieved by
essentially depleting all free ammonia available and extractions
The effect of oxidation air rate and air distribution from 40 per cent to nearly 50 per cent can be achieved by
maintaining at least 6 gpl of free ammonia in the discharge
In Campaigns 1 and 2, high oxidation air rates (up to 500 per cent solution.
of stoichiometric requirements) were used unsuccessfully trying
to increase copper extraction. Using large amounts of excess air

36 Sydney, 17 -18 May 1995 World's Best Practice in Mining and Processing Conference

Copper Extraction - %
50 ..:...:...::.....:..~------------------,
(Total Ammonia/Copper Molar Ratio
FIG 9 - Effect of particle size.
Sulphur oxidation
A key feature of the Escondida process is the extraction of some
copper contained in copper concentrates without significant
oxidation of sulphur to sulphate. A significant build-up of
sulphate in the recircled ammoniacal solution is thus avoided.
The total sulphate concentration, as shown in Figure 14,
increased slightly through the course of the campaign, an increase
of 0.076 gpVhr.
Overall performance
Piloting of the Escondida process defined the operating
conditions required for a +40 per cent copper extraction for all
four bulk concentrate samples. Once ammonia make-up rates
were matched to system losses through continuous aqua ammonia
additions, copper extraction could be predictably maintained.
Leaching times of approximately two hours are required when
oxidation air is well-dispersed in the leach pulp. Air hold-up in
the leach pulp was measured at 15 vol per cent. Oxidation air is
efficiently utilised in the well-agitated system, as near
stoichiometric air flows achieved the necessary 35 - 40 per cent
copper extraction.
RESIDUE FLOTATION
As copper is removed in the concentrate leaching step of the
process, leach residues are downgraded by about 12 copper
percentage units when 40 per cent of the copper is extracted.
Early laboratory flotation work on leach residues demonstrated
World's Best Practice in Mining and Processing Conference Sydney, 17 - 18 May 1995
THE DEVELOPMENT OF THE ESCONDIDA LEACH PROCESS
= 2.64)
that copper upgrading was feasible at the expense of only minor
copper losses. Results of these investigations showed that residue
flotation would restore the copper grade of residues to the
original incoming feed grade with losses to flotation tailings of
about two per cent of copper in residue. Residue flotation is
therefore considered not only to be profitable and to be a stand
alone operation, but to also provide an opportunity to produce a
high-grade concentrate favorable for marketing. As noted before,
unprocessed Escondida concentrates will have for certain clients
too much copper and a fuel value too low for effective smelting.
Pilot plant flotation
The pilot flotation section consisted of a four-cell rougher bank in
series with a four-cell scavenger bank, and three cleaner banks
consisting of four, two and two cells each, respectively. The
scavenger concentrate was either returned to the head of rougher
or combined with the rougher concentrate and sent to the first
cleaner. Flotation feed consisted of the leach residue filter cake
from the leaching section of the pilot plant. The filter cake was
washed and repulped two to three times to simulate an efficient
washing circuit. The washing media investigated included water,
dilute sulphuric acid, and raffinate (rc-m the SX section of the
pilot plant followed by water washing. Campaigns with no filter
cake washing were also performed. The pulp pH was adjusted to
11.0 with lime before rougher flotation. After about 15 minutes
of conditioning with Aero 238 and MIBC, the pulp was fed to the
rougher cells. The rougher concentrate was then subjected to
one, two or three stages of cleaning. Averaged results from
representative pilot campaigns for each of the concentrate
samples MI, M2, M3, and M4 are summarised in Table 7.
37
 WILLEM P C DUYVESTEYN

Copper Extraction - %
50 r - - - - - - - - - - - - - - - - - - - - - - - - ,
0
0

40
0
0

0

0

0

ff
30 0

~
20

0
0 0 22C

10 ~ 42C
0
~ 66C

0
0 10 20 30 40 50 60 70 80 90 100 110 120
Leach Time - min
Fia 10 - Effect of leaching temperature.

TABLES SOLVENT EXTRACTION

Composition ofpilot plant feed materials.
The solvent extraction section of the Escondida process serves
primarily as a 'media transfer' mechanism for copper.
Element (wt%) Sample Essentially, solvent extraction is used to move copper from an
MI M2 M3 M4 ammoniacal aqueous environment to an acidic sulphate solution
Cu 35.36 41.15 48.86 38.02
for electrowinning. Its purification function is secondary as few
troublesome impurity elements present in feed concentrates are
Au (ppm) 2.21 1.96 3.16 1.93
solubilised in the mild leaching environment of the Escondida
Ag (ppm) 64.3 107.3 81.3 84.3 process. Initial laboratory work had shown that LIX-54 was
Mo 0.104 0.155 0.175 0.093 preferred to LIX-84. Furthermore, a 75 vol per cent LIX-54 with
Fe 20.6 16.2 11.9 17.2 25 per cent kerosene as diluent was the optimum configuration.
S 31.8 28.4 25.6 29.3
Si 1.9 3.4 3.3 3.4 Pilot plant performance of LIX-54 system
As 0.071 0.177 0.056 0.148 The solvent extraction section of the pilot plant operated
Pb 0.020 0.013 0.010 0.020 predictably and without major or unforeseen problems. Pilot
Hg(ppm) 0 0 0 0 plant solvent extraction performance was evaluated in terms of
Zn 0.093 0.060 0.043 0.107 reliability (on-stream time), system capacity (organic phase
Ca 0.067 0.085 0.101 0.092 loading and stripping), impurity isolation (transfer of impurities
from raffinate through the organic phase to the EW electrolyte)
M2 0.043 0.061 0.066 0.069
and media isolation (entrainment and washing stage
performance).
It should be noted that the average leach feed grade was 40.9 The LIX-54 extraction system is currently used successfully by
per cent Cu with a corresponding leach residue grade of 28.3 per others on a commercial basis and is well understood in terms of
cent Cu. This represents 40 per cent copper extraction in the extraction chemistry. The LIX-54 system, as applied to the
leaching section of the pilot plant. The average flotation Escondida process, was also studied during extensive bench-scale
concentrate grade was identical to the leach feed grade at 40.9 per work in BHP Minerals' Laboratory. The pilot plant system was
cent Cu. A float recovery of 97.8 per cent Cu was achieved with designed and operated based on both information and experience
about 33 per cent weight rejection to tails.

38 Sydney, 1718 May 1995 World's Best Practice in Mining and Processing Conference
 THE DEVELOPMENT OF THE ESCONDIDA LEACH PROCESS

Copper Extraction - %
5 0 , . . - - - - - - - - - - - - - - - - - - - - - - -.....

40

30

20
M1: Cc
M2: Cc-Py
10 M3: Cpy-Cc-Cv
V M4: Py-Cc
Ol-__ ....I..-_ _.....I...._ _.....L..._ _.....L.._ _......L._ _---l._ _- " '_ _- - - '

o 15 30 45 60 75 90 105 120
Leaching Time - minutes

FIG 11 - Batch leaching of ml, m2, m3 and m4 concentrate samples.

TABLE 6
Overview vf leaching results.

Campai2I1 Number 1 2 3 4 5 6 7 8 9 10 11 12
Type Concentrate MI M2 MI M2 M3 M3 MI+M2 M4 M4 M4 MI+M3 M3
Duration - hours 102 102 98 96 117 99 93 47 71 34 57 46
On-Stream Factor .87 .99 .95 1.0 .96 1.0 .81 1.0 1.0 .97 .95 1.0
Cu Extraction - % 27.2 32.9 40.4 35.0 36.9 36.7 40.9 46.6 40.9 38.6 38.2 45.9

gained in mini pilot plant operation as well as guidance from the

Copper Extraction - % Ammonia Addition - kg/hr manufacturers of LIX@ reagents. The nominal set of operating
~ 3 conditions and system parameters used throughout the pilot plant
program are listed in Table 8.

ELECTROWINNING
Electrowinning cJf copper from sulphate solutions has been
practiced for over 100 years, but this technology has only
30 recently come to the forefront as a method for the production of
premium copper. With over 30 SX-EW plants presently
20 1 operating, the SX-EW product commands over 20 per cent of
the cathode market with continued increases in this share
Cop_ Eatfactlon ..
expected. All impurities, except oxygen and sulphur, are
10 generally lower in SX-EW copper than in electrorefined copper.
IIIH3 Adclltlon ,Ilw
In particular, the concentrations of detrimental elements such as
o L---'_~_---l.--==::;:==:::::;:==::::::;:==~ 0 selenium, tellurium, bismuth and arsenic are up to an order of
o 10 20 30 40 50 ~ 70 magnitude lower in SX-EW copper. Some companies are now
Elapsed Time - hrs producing 'five nines' copper (99.999 per cent Cui, indicating
that the total impurity load is less than ten parts per million,
FIG 12 - Copper extraction profile of campaign 9. excluding oxygen.

World's Best Practice in Mining and Processing Conference Sydney, 17 - 18 May 1995 39
WILLEM P C DUYVESTEYN

Free Ammonia in Leach Discharge - gpl

10 r----------------------.
9

o L~aa-----~
30 35
....40
;a----I....----...-.J
45 50
Copper extraction - %

FIG 13 - Free amrnonia.requirement for leach discharge.

40 Sydney, 17 - 18 May 1995 World's Best Practice in Mining and Processing Conference
 THE DEVELOPMENT OF THE ESCONDlDA LEACH PROCESS

TABLE 9
100 Sulfate - gpl Thiosulfate - gpl Impurity levels in cathode copper.
1.0

80 a - yy
aaa a
ua
a
aY
.. 0.8 Impurity
Element
LME
Grade A
Escondida
Pilot Plant
Escondida Escondida
Comm Plant Comm Plant

60
aa
0.6
(ppm)
Pb
Copper
5
Copper
<I
Copper (A) CODDer(B)
1.1 <0.8

40 --- Sullele

Thloeullele
Fe
S
IQ
15
2-3
2 - 10
2.1
7.5
0.1
0.6

20 ...
0.4

0.2
Se
Bi
Sb
2
2
4
<0.1
<0.1
<I
NA
NA
NA
<0.2
<0.1
< 0.1

o o
Te
As 5
- <I
<0.1
NA
NA
<0.2
<0.1
o 20 40 60 80 Ag - - <0.1 <0.1
Operating Time - hrs Zn - - <0.1 <0.1

FIG 14 - Sulphate and thiosulphate in leach solution. TABLE 10

Major equipment at the Cathode Leach Plant, Coloso, Chile.

TABLE 7
Plant Section Equipment Number Size
Summary of MJ, M2, M3 arul M4 flotation results.
Leaching Feed Thickener I lOOm dia
2
Belt Filters 3 63m
Grade- % Cu Recovery- % Leach Tanks 2 6.3 m dia by 9.1 m ht
Sample Leach Leach Tails Concentrate Copper Weight 2 8.7 m dia by 9.1 m ht
Feed Residue
Leach Agitators 3 260 kW
MI 35.4 23.0 1.14 35.8 98.2 61.8
I 150 kW
M2 40.8 29.6 1.71 43.6 98.0 33.6
Wash Thickeners 2 25 ID dia
M3 48.2 34.3 3.89 41.8 97.8 22.0
Clarifier I 8mdiaby9.1 mht
M4 39.2 26.2 1.77 42.2 97.3 40.0
Solvent Extraction Settlers 4 169 m3
Avera/?:e 40.9 28.3 2.13 41.3 97.8 34.2
Mixers 4 29m3
Storage Tanks 2 29OOm 3
TABLE 8 Column Cells 3 5.4m3
Solvent extraction operating parameters Cell House Lines 2 42 kA at 297 V DC
Residue Flotation Float Cells 14 28.3 m3

ODeratinl! Parameter Value

Extractant LlX-54 in kerosene 75 v/% Results from pilot plant operations and commercial operations
Loaded capacity (gpl Cu) 30 show that the Escondida process can produce even better than
'five nines' copper. A comparison of typical cathode copper
Extraction
analyses for pilot plant, two Escondida commercial plant samples
Number of stages 2
and LME specifications are shown in Table 9. The (B) sample
a/A (internal) I - 1.2 shows that the cathode is close to a 'six nines' specification.
a/A (external) I - 1.2
Intrastage recycle None UPDATE OF CURRENT STATUS OF THE
Settler area per stage (m2) 0.23 CATHODE LEACH PLANT
Organic flow rate (lIhr) 110 - 150
The cathode plant was started up in mid-November 1994. Table
10 gives a summary of the major pieces of equipment that are in
Washing Number of stages I or 2 use.
a/A (internal) I The plant was designed to produce 80 000 tpa cathode copper
a/A (external) 10 from 500 000 tpa copper concentrates. The nominal investment
Intrastage recycle Aqueous amounted to around US $160 million. The operating costs are
Settler area per stage (m2) 0.23 projected to amount to around 15 cents per pound of copper.
Control pH for acid addition 5 The start-up of the plant did not go as smoothly as anticipated.
First the leach tanks agitators were equipped with stabiliser
blades. Soon after start-up these blades detached themselves,
Stripping Number of stages I which resulted in damaged agitator shafts. At one point three out
a/A (internal) 0.8 of four leach reactors were out of service. A problem associated
a/A (external) 0.8 with the ammonia recovery system resulted in significant plant
Intrastate recycle None
down time. This part of the process was not piloted and
technology and support were obtained through a third party with
Settler area persta/?:e (m2) 0.23 significant experience in this field. Escondida staff solved this
problem.

World's Best Practice in Mining and Processing Conference Sydney, 17 - 18 May 1995 41
 WILLEM P C DUYVESTEYN
Solution clarification was carried out in a 'Double Yee'
clarifier, technology used elsewhere in the copper SX industry.
At the time of writing the clarifier unit does not function yet and
alternative ways of PLS cleaning are being evaluated. The
start-up of the solvent extraction plant was uneventful, until the
introduction of the clay treatment for removal of impurities from
the organic phase. This system acts differently in a basic
environment and long phase disengagement times and slow
kinetics will result if a cautious approach is not considered.
It took longer than anticipated for the leach to reach design
capacity. This was related to inefficiencies in the design of the
transfer of aerated pulp from leach tank to leach and to the
residue thickener. Work is presently underway to rectify this.
The residue flotation plant has not yet been started as there is
no need at this time to upgrade the residue. On occasion the
cathode leach plant feed has been as high as 50 per cent Cu which
resulted in a residue with around 37 per cent Cu. This is within
the range of copper specification for concentrate sales. Once
lower grade concentrate is processed, the residue flotation section
will be started up.
Table 9 indicates that the process and the plant are capable of
producing a very high quality cathode product.
CONCLUSIONS
A novel hydrometallurgical process for treatment of copper
concentrates has been developed at BHP Minerals' Laboratory.
Development work on the Escondida process, concluded with
successful operation of an integrated leach-SX-EW pilot plant
and a residue upgrading flotation pilot plant, has shown that all
major process objectives were achieved.
Once certain mechanical deficiencies are corrected the plant
will reach its design capacity of 80 000 tpa copper cathodes.
High quality, better than 'five nines' copper cathode is being
42 Sydney, 1718 May 1995
produced demonstrating that the Escondida process and the
Coloso plant will be able to compete effectively in the premium
cathode market.
REFERENCES
Duyvesteyn, W PC and Sabacky, B J, 1993. The Escondida process for
copper concentrates, in Extractive Metallurgy of Copper, Nickel and
Cobalt, pp 881-910, (The Minerals, Metals and Materials Society:
Warrendale, USA).
Duyvesteyn, W P C and Hickman, R N, 1993. Treatment of copper
sulphide concentrate, United States Patent 5,176,802.
Ek, C, Frenay, J and Herman, J C, 1982. Oxidized copper phase
precipitation in ammoniacal leaching - The influence of ammonium
salt additions, Hydrornetallurgy, 8: 17-26.
Kuhn, M C, Arbiter, N and Kling, H, 1974. Anaconda's Arbiter process
for copper, CIM Bulletin, 67:62-73.
Majima, H and Peters E, 1966. Oxidation rates of sulphide
minerals by aqueous oxidation at elevated temperatures, Trans
AlME. pp 1409-1413.
Mao, M H and Peters, E, 1982. Acid pressure leaching of chalcocite,
HYDROMETALLURGY Research, Development and Plant Practice,
pp 243-260, (The Minerals, Metals and Materials Society:
Warrendale, USA).
Peters, E, Warren, I H and Veltrnan, H, 1972. Extractive
Hydrometallurgy: Theory and Practice, Tutorial Symposium, Ed: M
T Hepworth, ( University of Denver).
Peters, E, 1976. Leaching of Sulphides, in Symposium on
Hydrometallurgy, Chapter 26 (AIME: New York).
Stanczyk, M H and Rampacek, C, 1966. Oxidation leaching of copper
sulphides in ammoniacal pulps at elevated temperatures and
pressures, Report of Investigation 6808, (USBM, Washington).
Tozawa, K, Umetsu, Y and Sato, K, 1976. On the chemistry of ammonia
leaching of copper concentrates, in Extractive Metallurgy of Copper
11, pp 706-721 (AIME: New York).
World's Best Practice in Mining and Processing Conference