Hydrometallurgy 83 (2006) 10 20

www.elsevier.com/locate/hydromet

Copper leaching from primary sulfides: Options for biological and

chemical extraction of copper
David Dreisinger
University of British Columbia, Department of Materials Engineering, 309-6350 Stores Road, Vancouver, B.C., Canada V6T 1Z4
Available online 2 May 2006

Abstract
The primary sulfide minerals of copper have been difficult to leach for the purpose of direct copper extraction. In particular,
chalcopyrite has been observed to undergo a type of passivation under a variety of oxidative leaching conditions.
Over the last 1015 years, a variety of biological and chemical leaching processes have emerged for overcoming the passivation
of chalcopyrite. A number of these processes are now entering commercial production or are approaching this status. The
BIOCOP process of BHP Billiton has now been commercialized at the Alliance Copper plant in Chile. The Total Pressure
Oxidation technology has been implemented by Phelps Dodge at Bagdad, Arizona. The Mt. Gordon copper process and the Sepon
copper process both use autoclave processes in the overall metallurgical circuit. In the Mt. Gordon circuit, the autoclave was used
to leach copper while at Sepon the autoclave is used to produce acid and ferric sulfate to meet the requirements of an atmospheric
leach. CESL and CVRD have completed a feasibility study to apply the CESL copper process in Brazil. PLATSOL technology
for copper, nickel, cobalt and precious metal recovery is now under final feasibility study for application by PolyMet Mining at the
NorthMet deposit in Minnesota, USA.
The number of available options for copper recovery from primary sulfides is multiplying. In addition to the above options
utilizing stirred reactor leaching, a number of heap leach options for primary sulfides are also emerging. For this paper, the various
processes for copper extraction from concentrate were reviewed, including the underlying mechanisms of leaching, followed by a
comparison of the advantages and disadvantages of selected process options.
2006 Elsevier B.V. All rights reserved.
Keywords: Chemical and biological leaching; Autoclave; Copper; Acid

1. Introduction
The treatment of copper concentrates by smelting
converting and electrorefining has dominated the copper
industry since the 1800s. Research and development in
searching for hydrometallurgical alternatives to traditional pyrometallurgy processes has intensified in recent
years. A whole range of chemical and biological

E-mail address: drei@interchange.ubc.ca.

0304-386X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2006.03.032

processes for copper recovery from concentrates have

emerged [121]. These processes are all successful in
(1) dissolving copper from chalcopyrite concentrates,
(2) purifying the leach solutions using modern separation processes and (3) recovering a high value, high
purity copper metal product.
The processes under development can be divided into
predominantly sulfate and chloride processes. Within
the sulfate grouping, processes can be sub-grouped as
either atmospheric or super-atmospheric in pressure and
chemical or biological in the leaching process.

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

There are a large number of reasons for pursuing

alternatives to conventional processing.
1. Capital Cost. The capital cost of smelter and refinery
complexes is very high. The typical range of cost is
$3000$5000 (USD) investment per annual tonne of
copper production (e.g. $900 Million to $1.5 Billion
for 300,000 tpy Cu production).
2. Impurity Tolerance. Smelters are limited in ability to
treat concentrates that contain high levels of
deleterious impurities.
3. CopperGold Concentrates. Gold is frequently
associated with copper concentrates. In some cases,
high recovery of gold by flotation is accompanied by
high levels of pyrite flotation resulting in a low grade
copper concentrate for treatment.
4. Mine to Market Optimization. It may make sense to
the overall economics of a mining operation to
account for (1) production of a lower grade
concentrate with higher overall recovery of copper
from the mine, (2) treatment of the lower grade
copper concentrate at the minesite to make copper
metal and; (3) use of by-product weak acid from the
copper recovery process as a reagent to leach and
recover copper at the Minesite. The overall economics to be achieved using this approach may give an
advantage to an alternative to smelting.
5. Recovery of Valuable By-Products. Copper concentrates may often contain significant levels of base and
precious metal by-products. Copper smelters are
efficient at recovery of gold, silver and PGM's but
often pay poorly and with much delay for these
elements.
6. Use of Existing Capital. In selected cases, copper
heap leach-SX/EW process plants are running out of
ore feed. These plants have fully functional SX/EW
plants available for further copper recovery as
electrowon cathode. In this case, it may make sense
to adopt a copper concentrate hydrometallurgy
process as the front end of the process plant and
further utilize existing capital.
7. Economics. Smelter economics are more scale
sensitive than hydrometallurgical alternatives. Hydrometallurgical plants may be more suited to
application of modular incremental project development if required.
Copper hydrometallurgy has been extensively
studied as an alternative route to chalcopyrite
concentrate treatment. The challenge of process
development for chalcopyrite leaching in sulfate
media is generally to leach chalcopyrite quickly and

11

completely with high yield of elemental sulfur. A

high yield of elemental sulfur leads to reduced costs
for oxygen or air for mineral leaching and reduced
neutralization/acid disposal costs. To overcome the
slow and incomplete leaching of chalcopyrite at lower
temperature, the two problems of (1) passive films on
the chalcopyrite surface and (2) the potential blocking
and wetting of chalcopyrite by liquid elemental sulfur
must be addressed. Historically, a large number of
hydrometallurgical treatment processes have been
developed to treat copper concentrates. These processes have all failed to achieve sustained commercial
production due to one or more of the following list of
challenges:
1. Low copper recovery in the primary leach step.
2. Copper loss due to copper co-precipitation with iron
hydrolysis products.
3. Difficult or incomplete precious metal recovery from
leach residue.
4. Unconventional and difficult electrolysis step.
5. Difficult elemental sulfur recovery step from leach
residue.
6. Excessive corrosion (especially chloride circuits).
7. Difficulty in fixing toxic by-products in a stable
waste product.
8. Large energy requirements for mixing and oxygen
dispersion.
9. Poor quality copper product that requires electrorefining.
Additional factors are often involved in preventing
advancement of new technologies. These include:
1. New technology risk. Many of the new processes
have unique chemistry, processing conditions or
equipment. These processes have not had adequate
commercial demonstration to mitigate risk.
2. Cost of licensing. The potential cost of licensing new
technology while also assuming the risk of being first
to commercially practice can mitigate against new
technology selection.
Against this backdrop, significant advances have
been made over the last few years in advancing the use
of hydrometallurgy for copper ore and concentrate
treatment. The historical and current developments are
discussed in references [121]. Table 1 lists the major
sulfate-based processes.
At least four separate sulfate-based commercial
plants have started or are under construction for copper
recovery. These include the Mt. Gordon Copper Process
[4,5], Phelps Dodge Total Pressure Oxidation [6,9],

12

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

Table 1
Sulfate-based copper hydrometallurgy processes for ore or concentrate treatment
Process

Status

Temperature
(C)

Pressure
(atm)

Regrind D80
(m)

Activox process [3]

90110

1012

510

Albion process [16,17]

85

510

Anglo American
University of British
Columbia Process
[1114]
Bactech/Mintek
low temperature
bioleach [18]
BIOCOP process [7]
CESL copper
process [2]
Dynatec
process [1921]
Mt. Gordon
process [4,5]
PLATSOL
process [15]

150

1012

35

C
D

6580
140150

1
1012

37
37

150

1012

37

90

220230

3040

15

Sepon copper
process [8]

P and
soon C

Atm
3040

100
50

Total pressure oxidation

process [6,9]

80 Copper
220230
Pyrite
200230

3040

37

1015

510

100

Special
conditions
Fine grinding combined with high oxygen
overpressure overcomes chalcopyrite passivation
Atmospheric ferric leaching of
very finely ground concentrate
Modest regrind combined with
surfactants for chalcopyrite leaching

Low T bioleach (3550 C) requires very fine

grind to overcome chalcopyrite passivation.
High T bioleach (6580 C) uses thermophilic bacteria
Chloride catalyzed leach of chalcopyrite producing
basic copper sulfate precipitate in the autoclave
Chalcopyrite is leached using
low grade coal as an additive
Pressure oxidation of chalcocite/pyrite ore or
bulk concentrate in an iron sulfate rich electrolyte
Total pressure oxidation in the presence of
1020 g/L NaCl. Precious metals leached at
the same time as base metals
Atmospheric ferric leach for copper from chalcocite.
Pressure oxidation of pyrite concentrate to make
acid and ferric sulfate for copper leach
Extreme conditions of T and P designed to
rapidly destroy chalcopyrite and other sulfides

Status: P = pilot plant, D = demo plant, C = commercial facility.

Alliance Copper BIOCOP Process [7], and the

Oxiana Sepon Copper Process. Phelps Dodge has
recently announced the expansion of concentrate
treatment to the Morenci, Arizona copper facility. The
Mt. Gordon, Total Pressure Oxidation, BIOCOP and
Sepon Processes are described below. In addition a short
description of the Anglo American Corporation
University of British Columbia process has also been
included.
1.1. The Mount Gordon Copper Process
The Mt. Gordon Copper Process was developed to
treat chalcocite ores from the historic Gunpowder
deposit in Northern Queensland, Australia. The
process uses low temperature pressure oxidation to
directly leach copper from the ore followed by SX/
EW of copper from the resulting leach solution. The
plant operation achieved an annualized copper production of 50,000 tonnes Cu as LME grade cathode in
2002.
The choice of pressure oxidation for this application
was driven by necessity. Flotation of the ore to produce
high-grade concentrates was trialed but was unsuccess-

ful due to very close association between copper and

barren pyrites in the ore. Heap leaching was rejected due
to expected lower recoveries (compared to agitation
leach) and concern about oxidation of the barren pyrite
with resulting formation of large excesses of acid.
Atmospheric ferric sulfate leaching was rejected due to
concerns about ferric regeneration and the inefficiency
of oxygen/air use in atmospheric processing.
In this process, chalcocite first leaches to form a
covellite reaction product and then the covellite
product leaches to form soluble copper and elemental
sulfur. Ferric ion is regenerated by oxygen in situ in
the autoclave. Other copper minerals will also leach
with oxygen in the presence of a ferric/ferrous
solution. In addition to the reactions involving the
copper minerals, pyrite in the ore will also oxidize to a
limited extent (23%). This minor oxidation is
beneficial in regenerating soluble iron and acid for
the leach system. The leached copper sulfate is
forwarded to solvent extraction and electrowinning of
copper cathode.
Crushed and milled ore is delivered in the form of a
thickened slurry to the plant, where it is dewatered on an
80 m2 horizontal filter belt to moisture of 1418%.

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

Filtration before leaching is important to maintain the

overall leach circuit water balance and to avoid
excessive dilution of the leach liquor.
Filter cake is re-pulped and the resulting slurry is
pumped into two parallel duplex stainless steel autoclaves each of 180 m3 total volume and 120 m3 working
volume. Each autoclave consists of five compartments
agitated by dual impellors using bottom Rushton
turbines and upper axial flow impellors. The leach
reactions are exothermic and the temperature profile in
the autoclave ranges from 77 to 80 C at the feed and to
8590 C at the discharge. A quantity of unheated
raffinate is injected into the third compartment to flatten
the temperature profile. The resulting control of
temperature has allowed for more efficient use of
oxygen for copper leaching and hence improved
autoclave leach rates.
Oxygen is supplied from two BOC VSA oxygen
plants of total 80 tpd capacity at 93% O2. Oxygen is
injected into the first three compartments to maintain a
total pressure of 7.7 bar and an oxygen partial pressure
of 4.2 bar.
Typical plant feed rates are 76 tph of solids at 8.8%
Cu. Raffinate flows are 240 m3/h to produce a PLS
grade of 35 g/l Cu. Leach recoveries vary with feed
mineralogy but are currently 9193% to produce a total
plant recovery of 90% after allowing for subsequent
wash recovery loss.
Autoclave residence time is about 60 minutes.
Leach slurry is discharged from the autoclave via two
small letdown pots and then flows through to four
atmospheric leach tanks each of 300 m3 working
volume. A further 12% copper is leached in these
tanks by the residual ferric sulfate in solution. The
product slurry is cooled and thickened in a hydroclassifier. The hydroclassifier underflow is filtered and
washed using a belt filter. Fine solids are removed from
the hydroclassifier underflow a pinned bed clarifier.
The PLS is then treated by a copper SX system and
electrowon using the ISA Process system for plating
and stripping.
The transfer of iron to the copper electrowinning
circuit by entrainment through SX necessitates bleeding
of EW electrolyte and costs for acid and cobalt sulfate
makeup and neutralization of excess acid. A Fenix Iron
Removal system [22] for ion exchange iron removal
from copper electrowinning was installed and successfully operated at Mt. Gordon as a replacement for most
of the bleeding of electrolyte.
The capital cost of the plant was $112.7 Million AUD
(or $57.5 Million USD at 0.51 exchange rate). The site
operating cost for ore through to metal were reported to

13

be $0.31 USD/lb of copper, one of the lowest cost

operations in the world. The Mt. Gordon copper leach
and process plant was shut down in 2004 due to change
of ore type (no longer Esperanza chalcocite/pyrite) and
corporate change of ownership to the Birla company
from India.
1.2. The total pressure oxidation process
The total pressure oxidation process uses high
temperature and pressure oxidation conditions to
oxidize all sulfide minerals to sulfates and sulfuric
acid. Conveniently, total pressure oxidation also
results in iron precipitation as hematite. Total pressure
oxidation plants operated in the US in the 1950s for
recovery of copper, cobalt and nickel from complex
ores [2326] so this technology is not regarded as
new.
Phelps Dodge has now revitalized the large-scale
application of total pressure oxidation at the Bagdad
plant in Arizona. At this facility approximately
16,000 tpa of Cu can be recovered from concentrates
that previously were sent to a smelter facility. Under
total oxidation conditions, 140 short tons of acid are
produced per day for application to the stockpile leach
operation at Bagdad. In this way, an acid credit is
derived.
A single autoclave is used to leach the concentrates which then proceed to flashing (to return the
slurry to atmospheric pressure), slurry cooling, CCD
washing and then copper SX/EW. The autoclave
stream is merged with the stockpile leach solution
stream to provide a combined PLS feed to the SX/
EW facility. The acid from the autoclave process is
then recycled in the SX raffinate back to the stockpile
leach.
The washed autoclave residue is neutralized with
lime in 4 stages. If precious metals were present (very
low precious metals in the Bagdad concentrate), the
neutralized residue could be cyanide leached.
The total pressure oxidation process is very suitable
for application where the acid from pressure leaching
can be used beneficially. The process has been
commercially demonstrated at a large-scale and could
easily be scaled up to larger size if required. Total
pressure oxidation for copper concentrate treatment
should now be regarded as proven technology.
1.3. The BIOCOPTM process
The BIOCOP process was developed by the BHP
Billiton biotechnologies group based in Johannesburg,

14

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

South Africa. The process uses thermophile bacteria to

oxidize and leach copper from sulfide concentrates. The
thermophile bacteria oxidize sulfide minerals to metal
sulfates and sulfuric acid at temperatures of 6580 C.
The BIOCOP flow sheet has a number of interesting
features:
Oxygen is used for bioleaching. This necessitates the
provision of an oxygen plant. Previously, bioleach
plants for gold and base metal applications were
operated with air blowers.
pH control is necessary during leaching to prevent
too low a pH level in leaching
Arsenic may be removed in a separate step to
produce a residue for disposal.
Copper may be recovered by SX/EW. Excess acid
may be used in heap leaching if appropriate.
The Alliance Copper joint venture group (BHP
Billiton and Codelco) have commercialized the
process in Chile. A 20,000 tpa Cu plant has been
built close to Chuquicamata with the long term goal
of treating arsenical concentrates from the Mansa
Mina deposit. The plant is integrated with a heap
leach circuit to allow for an acid credit back to the
bioleach plant. The BIOCOP process is therefore
similar to the Total Pressure Oxidation Process
described above in that high copper extractions are
achieved under total oxidation conditions (to sulfates).
The major difference seems to be in the availability of
acid after copper solvent extraction. In the bioleach
process, partial acid neutralization is practiced in the
two-stage bioleach using limestone addition to the
bioleach slurry. This neutralization incurs an operating
cost that is not present in total oxidation and
effectively reduces the available acid credit from the
bioleach process. Nevertheless, for specific applications, the bioleach approach may be favoured relative
to pressure leaching. Clearly, the successful startup of
the Alliance Copper project in Chile has validated the
technology at a significant scale. Bioleaching of
copper concentrates is now regarded as a proven
technology.
1.4. The Sepon Copper Process
The Sepon Copper Process was developed for the
recovery of copper from the Sepon copper deposit in
Laos. The mineralogy of Sepon is complex. Copper is
present mainly as chalcocite with pyrite and a large
component of clay mineralization. The flow sheet
involves atmospheric acid ferric sulfate leaching of

copper followed by residue washing (first in raffinate

and then in water) and pyrite/elemental sulfur flotation.
The key development in this flow sheet is the
autoclave treatment of the flotation concentrate containing pyrite and elemental sulfur. The autoclave
process produces a basic ferric sulfate product (as
opposed to the usual hematite product). The basic
ferric sulfate product can then be re-leached to produce
a strong ferric sulfate solution for application to
atmospheric leaching.
The other benefit of the Sepon process is the
possibility of scavenging any remaining copper minerals
in the pyrite float concentrate (that were not leached in
the atmospheric leach). These copper minerals would be
expected to leach under the total oxidation conditions
employed, thus increasing overall copper recovery from
the Sepon ore.
The Sepon copper plant has started up successfully in
March of 2005. The initial plant capacity is set for
60,000 tpa of copper. The autoclave oxidation of pyrite/
sulfur will provide virtually all acid and ferric sulfate
(and heat) required for the copper leaching process. The
process can be considered a hybrid of a copper leach
and pyrite oxidation process.
1.5. The Anglo American Corp./University of British
Columbia Copper Process
The Anglo American Corp./University of British
Columbia (AAC/UBC) Copper Process is a mediumtemperature leaching process for chalcopyrite concentrates. The concentrate is reground to fine size
(P80 520 m) and leached under moderate pressure
at 150 C in an acidsulfate system. The addition
of a surfactant disperses the molten elemental sulfur,
avoiding chalcopyrite passivation during leaching.
Copper is recovered by SX/EW to produce premium
copper cathode. The process is distinguished by
high copper extractions, hematite or jarosite formation, and elemental S as the dominant reaction
product.
The AAC/UBC process was recently evaluated in
a continuous, fully integrated pilot-plant trial. The
flow sheet comprised fine grinding of the concentrate,
pressure leaching, thickening and filtration, copper
SX/EW, with a bleed circuit to recover valuable base
metal co-products. Gold was recovered from the
autoclave residue by direct cyanidation. Copper and
zinc extractions above 95% and elemental sulfur
yields of 60% were achieved at 150 C in a 2-h
residence time. The presence of surfactants did not
affect the extraction of copper or the phase separation

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

15

Feed Slurry
Combined Raffinate

Vent
Copper Leach

Oxygen or Air

Leach Discharge

Primary Chalcopyrite Leaching

Flash Steam

Flash Letdown
(Optional)

Atmospheric Slurry

Fe - Cu Precipitate
Releach

Fe/Cu Rem. Solids

Releach + A/C Slurry

Slurry Cooling

Heat

Cooling and S/L Separation and

Washing

Cool Slurry

S-L Separation (CCD)

Wash Water

Cu PLS

Washed Residue

Oxygen
Copper Cathode

Cu SX - EW

Water
Acid Raff

Copper Separation and Recovery

Raffinate

Gas Vent
Limestone
Air

Acid Neutralization

Raffinate Splitter 1

Raff to Neut

Acid Neut Slurry

Gypsum Clarifier

Clarified Soln

Recycle Solids

Acid Neutralization and Control

Gypsum Slurry

Wash Water

Gypsum Filter

Gypsum Residue

Gypsum Filtrate

Neut Raff to A/C

Solution to Fe/Cu Removal
Gas Vent
Lime
Fe/Cu Removal

Secondary Copper Recovery

Air
Fe/Cu Removal Slurry

Fe/Cu Rem. Solids

Fe-Cu Thickener
Solution to BZS Precipitation
Gas Vent

Lime
Air

BZS Precipitation

Byproduct Recovery

BZS Slurry
BZS Barren Solution
BZS Filter
Basic Zinc Sulfate for Sale

Fig. 1. Generic process for chalcopyrite concentrate processing with neutralization of acid.

16

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

in the SX process. Gold extraction exceeded 80%.

The process is ready for industrial application and is
expected to be highly competitive with other
hydrometallurgical copper processes under commercial development.

process. The chemistry is abbreviated in the listing

below due to space constraints.
Copper leaching (primary leaching processes using
chemical or biological oxidation)
CuFeS2 O2 2H2 SO4 CuSO4 FeSO4
2H2 O 2S

2. Process design and heat and mass balances

The chemical and biological processes for chalcopyrite treatment are linked together by common
elements of process design. The sulfate-based processes
involve copper leaching, solidliquid separation and
residue washing, copper SX/EW and raffinate management. The raffinate management can involve partial
recycle and neutralization (for acid and copper
recovery) or partial recycle and bleed to an acidconsuming heap. Figs. 1 and 2 illustrate both these
approaches. The overall approach is based on flow
sheets reported for the Dynatec Copper Process [21].
The chemistry of the leaching processes can be
summarized according to the various steps in the

Cu3 AsS4 2:75O2 3H2 SO4 3CuSO4 4S

H3 AsO4 1:5H2 O
Cu5 FeS4 3O2 6H2 SO4 5CuSO4 4S
FeSO4 6H2 O
CuS 0:5O2 H2 SO4 CuSO4 S H2 O
Cu2 S O2 2H2 SO4 2CuSO4 S 2H2 O
ZnS 0:5O2 H2 SO4 ZnSO4 S H2 O
Fe7 S8 3:5O2 7H2 SO4 7FeSO4 8S 7H2 O

Feed Slurry
Combined Raffinate

Vent
Oxygen or Air

Copper Leach
Leach Discharge

Primary Chalcopyrite Leaching

Flash Steam

Flash Letdown
(Optional)

Atmospheric Slurry
Fe - Cu Precipitate
Releach

Releach + A/C Slurry

Slurry Cooling

Heat

Cooling and S/L Separation and

Washing

Cool Slurry

Wash Water

S-L Separation (CCD)

Cu PLS

Washed Residue

Oxygen
Copper Cathode

Water

Cu SX - EW

Copper Separation and Recovery

Raffinate
Acid Raff
Raffinate Splitter 1

Acid Neutralization and Control

Secondary Copper Recovery
Recycle Raffinate

Acid Consuming Heap

Leach and Cu SX/EW

Fig. 2. Generic process for chalcopyrite concentrate processing with bleed to associated heap leach.

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

FeS2 0:5O2 H2 SO4 FeSO4 2S H2 O

Fe2 SO4 3 2H3 AsO4 2FeAsO4 3H2 SO4
FeSO4 0:25O2 0:5H2 SO4 0:5Fe2 SO4 3
0:5H2 O
Fe2 SO4 3 3H2 OFe2 O3 3H2 SO4
Fe2 SO4 3 4H2 OFe2 O3d H2 O 3H2 SO4
1:5Fe2 SO4 3 7H2 OH3 OFe3 SO4 2 OH6
2:5H2 SO4
S 1:5O2 H2 OH2 SO4
FeCu Precipitate Releach (redissolve precipitated
copper and zinc from scavenger step)
H2 SO4 CaO H2 OCaSO4d 2H2 O
CuSO4d 2CuOH2 2H2 SO4 3CuSO4 4H2 O
ZnSO4d 2ZnOH2 2H2 SO4 3ZnSO4 4H2 O
Cu SX/EW (conventional recovery method for
copper)
Copper Extraction: CuSO4 2HRCuR2 H2 SO4
Copper Stripping: CuR2 H2 SO4 CuSO4 2HR
Copper Electrowinning: CuSO4 H2 OCu
0:5O2 g H2 SO4

17

Fe/Cu removal (precipitate for copper recovery and

recycle)
FeSO4 CaO 2:5H2 O 0:25O2
0:5Fe2 O3d H2 O CaSO4d 2H2 O
Fe2 SO4 3 3CaO 2H3 AsO4 3H2 O
2FeAsO4 3CaSO4d 2H2 O
Fe2 SO4 3 3CaO 7H2 O
Fe2 O3d H2 O 3CaSO4d 2H2 O
H2 SO4 CaO H2 OCaSO4d 2H2 O
3CuSO4 2CaO 6H2 O
CuSO4d 2CuOH2 2CaSO4d 2H2 O
3ZnSO4 2CaO 6H2 O
ZnSO4d 2ZnOH2 2CaSO4d 2H2 O
Basic zinc sulfate precipitation (secondary element
recovery in a potentially saleable form)
FeSO4 CaO 2:5H2 O 0:25O2
0:5Fe2 O3d H2 O CaSO4d 2H2 O
Fe2 SO4 3 3CaO 2H3 AsO4 3H2 O
2FeAsO4 3CaSO4d 2H2 O
Fe2 SO4 3 3CaO 7H2 O
Fe2 O3d H2 O 3CaSO4d 2H2 O
H2 SO4 CaO H2 OCaSO4d 2H2 O

Overall Reaction: CuSO4 H2 OCu 0:5O2 g

H2 SO4

3CuSO4 2CaO 6H2 OCuSO4d 2CuOH2

2CaSO4d 2H2 O

Acid neutralization (precipitate gypsum and small

amount of iron and copper)

3ZnSO4 2CaO 6H2 OZnSO4d 2ZnOH2

2CaSO4d 2H2 O:

FeSO4 CaCO3 2:5H2 O 0:25O2

0:5Fe2 O3d H2 O CaSO4d 2H2 O CO2
Fe2 SO4 3 3CaCO3 2H3 AsO4 3H2 O
2FeAsO4 3CaSO4d 2H2 O 3CO2
Fe2 SO4 3 3CaCO3 7H2 O
Fe2 O3d H2 O 3CO2 3CaSO4d 2H2 O
H2 SO4 CaCO3 H2 OCaSO4d 2H2 O CO2
3CuSO4 2CaCO3 6H2 O
CuSO4d 2CuOH2 2CaSO4d 2H2 O 2CO2

A copper concentrate of 27.5% copper was used as

an input to detailed heat and material balances for four
different processes; AACUBC, Bactech, BIOCOP
and Total Pressure Oxidation. The copper mineralogy
was predominantly chalcopyrite and bornite with minor
enargite, chalcocite and covellite.
CuFeS2
Cu2S
CuS
Cu5FeS4
CuFe2S3

%
%
%
%
%

59.01
3.41
0.41
6.02
0.00

Cu3AsS4
ZnS
FeS2
Al2O3

%
%
%
%

0.53
0.894
20.130
0.500

CaO
MgO
MoS2
SiO2

%
%
%
%

0.250
0.250
0.33
8.26

The modelling was done by choosing reasonable

process design criteria for each step of the process using

18

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

Table 2
Heat and material balance modelling of the chemical and biological processing of copper concentrates
Process

AACUBC

BACT.

BIOCOP

TPOX

AACUBC

BACT.

BIOCOP

TPOX

Bleed to heap
Leach temperature (C)
Limestone addition
Cooling in leach (MW)
Reagent constant (t/t Cu)
O2
Air
CaCO3
CaO
Acid in raffinate to heap
H2SO4 (t H2SO4/t Cu)

NO
150
No
0

NO
45
Yes
47.41

NO
75
Yes
39.9

NO
220
No
0

YES
150
No
0

YES
45
Yes
47.14

YES
75
Yes
40.1

YES
220
No
0

1.56
0.03
1.31
0.11

0.00
15.89
3.46
0.32

3.90
0.19
3.42
0.32

3.05
0.05
4.11
0.18

1.55
0.00
0.00
0.00

0.00
15.55
2.21
0.00

3.86
0.00
2.21
0.00

3.02
0.00
0.00
0.00

0.89

0.93

0.93

3.25

either flow sheet 1 or 2. Each of the processes was

assumed to give high overall copper extraction. The
results of the modelling are summarized in Table 2. This
table can be used to show the principle differences
between the processes.
The biological leaching processes (Bactech and
BIOCOP) consume limestone during leaching and
require indirect cooling of the bioreactors. The chemical
processes (AACUBC and TPOX) do not require
indirect cooling (cooling is provided by direct injection
of cool solutions) and do not consume limestone during
leaching.
The use of limestone in the AACUBC and TPOX
process relates to the neutralization of excess acid and
the precipitation of copper and iron. The relative amount
of limestone for AACUBC is much lower due to much
lower sulfate formation during the primary leach step.
The consumption of oxygen is highest for BIOCOP, and lower for TPOX and AACUBC. This
result is a function of total oxidation of sulfur to sulfate
assumed for BIOCOP and TPOX and partial
oxidation of sulfide to sulfate (balance is elemental
sulfur) for AACUBC. BIOCOP was assumed to
have a lower oxygen utilization due to atmospheric

tankage for leaching. The Bactech process consumes air,

not oxygen in leaching.
The production of acid for the processes that bleed to
the heap (Fig. 2 and Table 2) show modest levels of acid
by-product for AACUBC, Bactech and BIOCOP
(less than 1 t H2SO4/t Cu) and very high levels for
TPOX (3.25 t H2SO4/t Cu). The lower level for AAC
UBC is due to low sulfide to sulfate oxidation while
Bactech and BIOCOP are low due to acid neutralization during leaching. The TPOX process has the
highest overall acid generation capability for making
acid for a heap leach.
A further calculation can be made to compare the
relative economics of the various scenarios using only
the cost of consumables. The cost of consumables (and
the value of by-product acid) can vary widely but for the
purpose of this analysis costs/values of $50/t for
oxygen, $8/t for air, $30/t for limestone, $100/t for
lime and $100/t for acid. Table 3 highlights the cost
implications of the various mass balance consumptions/
credits for key reagents. Note that there are many other
costs for manpower, SX/EW, utilities, taxes, etc., that
must also be considered in the full costing of the
operation of the copper plant.

Table 3
Consumable costs and credits for chemical and biological processing of copper concentrates
Process

AACUBC

BACT.

BIOCOP

TPOX

AACUBC

BACT.

BIOCOP

TPOX

Bleed to heap
Reagent costs (USD/t Cu)
O2
Air
CaCO3
CaO
Acid credit (USD/t Cu)
H2SO4 (t H2SO4/t Cu)
Total (USD/t Cu)
Total (USD/lb of Cu)

NO

NO

NO

NO

YES

YES

YES

YES

78
0
39
11

0
127
104
32

195
2
103
32

153
0
123
18

78
0
0
0

0
124
66
0

193
0
66
0

151
0
0
0

0
129
0.058

0
263
0.120

0
331
0.151

0
294
0.134

89
12
0.005

93
98
0.044

93
166
0.076

325
174
0.079

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

The results of the analysis are very striking. For the

processes without a bleed to the heap, the AACUBC
process has the lowest unit cost due to less oxidation
of sulfur to sulfate and hence lower oxygen and
limestone costs. The Bactech, BIOCOP and TPOX
processes are all very close together in cost (within
3 cents/lb). For the processes that have a bleed to the
heap, the net cost for AACUBC is virtually zero,
indicating that the acid credit offsets the cost of
oxygen for pressure oxidation. The net cost for TPOX
is NEGATIVE 8 cents/lb indicating that the value of
the by-product acid (under the assumed economic
conditions) is greater than the cost of oxygen, even for
full oxidation. In contrast the costs for the Bactech
and BIOCOP processes range from net values of
about 4 to 8 cents per lb of Cu.
These results indicate some factors that will
influence use of different technologies under different
circumstances. For simple copper leaching from
chalcopyrite concentrates where no heap leach exists,
one might choose a process such as AACUBC (or
similar processes with reference to Table 1) for copper
recovery. For simple copper leaching from chalcopyrite concentrates with an associated heap leach, the
AACUBC process and the TPOX each give excellent
credits for acid. The choice of which process to
choose may come down to a consideration of acid
demand (i.e. the acid production ability of TPOX may
be excessive for the demands of the heap). For copper
leaching with for example a gold credit in the
concentrate and no heap leach, then any of the
Bactech, BIOCOP or TPOX processes may be
equally economically effective. Each of these processes can fully oxidize the concentrate, making the leach
residue amenable to cyanide recovery of gold. If the
situation presents as a coppergold concentrate with a
heap leach acid demand, then TPOX would be the
preferred alternative due to full oxidation (residue
amenable to gold recovery) and acid availability as a
by-product (again dependent on matching acid production with acid demand).
Of course there could be other technical, economic or
environmental reasons for choosing one process over
another for treatment of copper concentrates. It is the
author's opinion that the treatment of arsenical copper
gold concentrates are ideally suited to biological
treatment (as has been demonstrated in BIOCOP
testing) and that TPOX may have limited utility due to
formation of complex basic copper arsenates under
TPOX conditions. The formation of complex basic
arsenates limits copper extraction and inhibits gold
recovery.

19

3. Conclusions
Hydrometallurgical treatment of copper concentrates
using chemical and biological leaching is making
inroads to the field traditionally dominated by smelting
and refining. The field has tended to advance thus far by
necessity or unique opportunity. The Mt. Gordon and
Sepon processes were developed to recover copper from
ores that were not easily amenable to conventional
flotation. The total pressure oxidation process has been
commercialized by Phelps Dodge where the acid from
the total oxidation autoclave can be beneficially used in
the stockpile leach process at Bagdad. The BIOCOP
process has been applied to a unique opportunity at the
Chuquicamata complex in Chile.
It is predicted that further niche applications of
hydrometallurgy for concentrate treatment will continue
into the future. However, the industry is still waiting for
a technology that can compete on a total operating cost/
total capital cost and metal recovery basis with the
conventional smelting/refining process.
In this paper, selected examples of chemical and
biological processes in the sulfate system were compared and contrasted. Model flow sheets and simplified
heat/mass balances for a typical copper concentrate were
developed for cases with and without bleeding of
electrolyte to a heap leach for use of by-product acid.
The two chemical processes (AACUBC) and TPOX
were distinguished by whether sulfur was partially or
fully oxidized to sulfate and sulfuric acid. Both the
biological alternatives (Bactech and BIOCOP) fully
oxidized sulfur to sulfate. Where acid from the copper
leach was to be neutralized (no heap), the AACUBC
process had a clear advantage over TPOX and the
biological alternatives. For the model cases where acid
was a valuable by-product, the chemical alternatives
were superior to the biological processes due to higher
acid consumption (per unit of sulfur oxidized to sulfate)
as the biological processes require limestone addition
for pH control in leaching. The limestone addition,
neutralizes a portion of the acid formed, limiting the
value of the acid by-product.
The biological processes seem to have unique
application for coppergold concentrates where there
is no heap leach available to consume excess acid and/or
where the copper concentrates contain higher levels of
arsenic (for example, enargite mineral).
In summary, each process, whether chemical or
biological will have unique features and potential
advantages for each situation. The goal of this paper
was to highlight the quantitative analytical tools
required to compare and contrast these processes in

20

D. Dreisinger / Hydrometallurgy 83 (2006) 1020

order to make an informed selection for a particular

application.
[14]

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