Overview Copper and Nickel Production

Copper Leaching from Chalcopyrite

Concentrates
Shijie Wang

Chalcopyrite (CuFeS2) is one of the progress may be made. Minerals Company (CUPREX),6 Cyprus
most abundant copper-bearing minerals, Leaching processes in hydrometal- Metallurgical Processes Corporation
which accounts for approximately 70 lurgy are concerned mainly with treating (Cymet),7 as well as the new entries of
percent of the world’s known copper minerals in order to form a solution Intec Limited (INTEC)8,9 and Outo-
reserves. For more than 30 years, a containing the metals to be recovered. kumpu (HydroCopperTM)10,11 have dem-
significant number of processes have Chloride leaching has initially been onstrated significant potential for the
been developed to leach copper from found to be the best process for treating production of copper by the chloride
chalcopyrite concentrates. These pro- chalcopyrite concentrates under oxidiz- leaching process.
cesses recover copper via hydrometal- ing conditions in acid or alkaline solu- The principal chemical reactions in
lurgical leaching of the copper compo- tions. Bioleaching has historically the ferric chloride leaching of chalcopy-
nent of chalcopyrite concentrates, fol- recorded its ability to economically rite concentrate may be summarized as
lowed by solvent extraction and electro- process low-grade sulfide ores and to shown in Equations 1 and 2 (all equations
winning. A number of demonstration process ores that may not be feasible to are shown in Table I). The corresponding
plant operations have been conducted, smelt for environmental reasons. Pres- reactions for CuCl2 attack are given in
but as of this writing none of the processes sure sulfate leaching, which advances in Equations 3 and 4.
have become completely commercially chemical reaction kinetics, has naturally
The Cuprex Process
operational. been focused on treating chalcopyrite
concentrates in direct competition with The Cuprex process leaches chalco-
INTRODUCTION
smelting. pyrite concentrate at atmospheric pres-
Chalcopyrite is not only the most The current hydrometallurgical dem- sure with ferric chloride solution in two
abundant of the copper sulfides, but also onstration plants are mainly focused on stages. The pregnant liquor containing
the most stable mineral because of its bioleaching and pressure sulfate leaching copper, iron, and minor amounts of
structural configuration (face-centered chalcopyrite concentrates to produce impurities, mainly zinc, lead, and silver,
tetragonal lattice). It is also the most copper cathodes via conventional solvent is sent to the extraction stage of the SX
refractory to hydrometallurgical process- extraction (SX) and electrowinning circuit, where it is contacted at ambient
ing. In current practice, the recovery of (EW). Major problems of these leaching temperature with a kerosene solution of
copper from the sulfidic ores of chalco- processes are how to overcome a pas- DS5443. The copper, selectively trans-
pyrite involves subjecting the ores to a sivating layer that forms on the mineral ferred to the organic phase, is extracted
froth flotation operation that produces a surfaces during the leaching and how to in three stages and then stripped by
concentrate of the valuable metal sul- deal with excess production of sulfuric contacting water in another three
fides, which is then commonly smelted acid or elemental sulfur. stages.
and electrorefined to produce copper The aqueous solution of copper chlo-
CHLORIDE LEACHING
metal. ride is then sent to the electrolysis section
Due to interests that include environ- Only chlorides of metals in a higher as catholyte, which is fed to the cathode
mental aspects and the possibility of valence state, such as ferric or cupric compartment of an EW cell to produce
increased exploitation of mixed- and chloride, will leach metals from their granular copper. The SX and EW reac-
lower-grade ores and relatively small sulfides because oxidation is necessary. tions can be written as shown in Equa-
isolated deposits, there has been a world- Of the numerous chloride routes, ferric tions 5, 6, and 7. Electrowinning of
wide upsurge of interest in hydrometal- chloride (FeCl3) leaching of chalcopyrite copper from chloride solution takes place
lurgical processes for the production of concentrates, which was initiated by the in a diaphragm cell, where the cathode
copper. Hydrometallurgical processing U.S. Bureau of Mines’ Reno Metallurgy and anode compartments are separated
of chalcopyrite concentrates has received Research Center in 1969,1,2 received by a reinforced cation-selective ion-
considerable attention over the last three significant attention. The technologies exchange membrane. Chlorine generated
decades. The entry of copper giants developed by Duval Corporation at the anode is recovered and used to
Phelps Dodge, BHP Billiton, and (CLEAR),3–5 Imperial Chemical Indus- reoxidize the cuprous chloride generated
Codelco indicate that at long last real tries, Technicas Reunidas and the Nerco in the catholyte during EW.

48 JOM • July 2005

 catalyze the oxidation of iron sulfides to technology has progressed, the bioleach-
The Intec Process
create ferric sulfate and sulfuric acid. ing has moved to more processing-ame-
The Intec process involves a four-stage Two mechanisms are often quoted as nable methods via agitated leaching in
countercurrent leach with chloride/bro- direct and indirect mechanisms of bio- a tank and using thermophilic (high-
mide solution at atmospheric pressure. leaching. The direct mechanism relates temperature) microorganisms, which
Leach residue is filtered and discharged to the role of bacterial interaction with represent a major breakthrough in the
from stage 4 to waste, while copper-rich the minerals directly, where pyrite is bioleaching of chalcopyrite.
pregnant liquor leaves stage 1. Gold and broken down to ferrous iron and sulfide
The BioCOPTM Process
silver are solubilized along with copper. radical, in an acidic environment giving
Gold is recovered from solution through rise to leaching, which is expressed as BHP Billiton and Codelco built a
a carbon filter, and silver is cemented shown in Equations 13, 14, and 15. The demonstration plant at Chuquicamata,
along with mercury ions to form an indirect mechanism relates to the in north Chile.12 Constructed in a stirred
amalgam. Both of these are then further chemical oxidation of the minerals by reactor containing dilute sulfuric acid
treated for the recovery. Impurities in ferric iron generated by the bacteria. The into which air is blown, hyderthermo-
the liquor are precipitated with lime and bacteria gain energy by the ferrous-to- philic microorganisms, which operate at
removed by filtration. The purified ferric conversion shown in Equation a temperature between 60°C and 90°C,
copper solution is then electrowon to 16. are used. Limestone is added both to
produce pure copper metal and to regen- Typically, both mechanisms are pres- maintain the pH of the solution and to
erate the lixiviant for recycling in the ent and occur simultaneously in a bio- provide carbon dioxide for bacterial
leach section. An extremely important leaching environment. Modern com- growth. Nutrients are added to the reac-
feature of the process is that heat is mercial application of bioleaching began tor, followed by copper concentrate in
provided by the exothermic leach reac- in the 1950s at Kennecott’s Bingham an amount that provides a pregnant liquor
tions. This, along with the flow of air in mine near Salt Lake City, Utah. As the containing 30–40 g/L (which is reduced
the leach section, evaporates water and
keeps the water balance close to neutral
Table I. Equations
so no liquid effluent is produced from
the plant. Another equally important note CuFeS2 + 3FeCl3 → CuCl + 4FeCl2 + 2S0 (1)
is that all impurities including mercury CuFeS2 + 4FeCl3 → CuCl2 + 5FeCl2 + 2S0 (2)
are either recovered or stabilized.
CuFeS2 + 3CuCl2 → 4CuCl + FeCl2 + 2S0 (3)
The Outokumpu HydroCopper
Process S0 + 4H2O + 6CuCl2 → 6CuCl + 6HCl + H2SO4 (4)

As the newest patented technology, 2L(org) + Cu2+(aq) + 2Cl- (aq) → L2CuCl2(org) (5)
the Outokumpu process involves coun- L2CuCl2(org) → 2L(org) + Cu2+(aq) + 2Cl- (aq) (6)
tercurrent leaching of chalcopyrite
concentrates using air and chlorine as Cu2+(aq) + 2Cl- (aq) → Cu +Cl2 (7)
oxidants, as shown in Equation 8. After CuFeS2 + CuCl2 + 3/4O2 → 2CuCl + 1/2Fe2O3 + 2S (8)
leaching, the part-cuprous baring solu-
tion is oxidized by chlorine to cupric that CuCl + 1/2Cl2 → CuCl2 (9)
is recycled back in leaching, as shown CuCl + NaOH → 1/2Cu2O + NaCl +1/2H2O (10)
in Equation 9.
The remaining cuprous solution, after 1/2Cu2O + 1/2H2 → Cu +1/2H2O (11)
purification for silver and impurity 2NaCl + 2H2O → 2NaOH + Cl2 + H2 (12)
removal, is treated with sodium hydrox-
ide to precipitate cuprous oxide that is 2FeS2 + 7O2 + 2H2O → 2Fe2+ + 2SO42- + 2H2SO4 (13)
then reduced to metal. The unique pro- 2S + 3O2 + 2H2O → 2 H2SO4 (14)
cess produces (in a standard chloro-alkali
cell) and provides all of the chlorine, CuFeS2 + 4H+ → Cu2+ + 2Fe2+ + 2H2S (15)
sodium hydroxide, and hydrogen needed CuFeS2 + 4Fe3+ → Cu2+ + 5Fe2+ + S0 (16)
to operate, as shown in Equations 10,
11, and 12. 2CuFeS2 + 2.5O2 + 2H2SO4 → 2CuSO4 + Fe2O3 + 4S + 2H2O (partial oxidation) (17)

BIOLEACHING 2CuFeS2 + 8.5O2 + 2H2O → 2CuSO4 + Fe2O3 + 2H2SO4 (total oxidation) (18)

Bioleaching (bacterial leaching), 2FeS2 + 8.5O2 + 4H2O → Fe2O3 + 4 H2SO4 (total oxidation) (19)
associated with a biooxidation (bacterial 3CuFeS2 + 7.5O2 + H2O + H2SO4 → CuSO4·2Cu(OH)2 + 1.5Fe2O3 + 6S (20)
oxidation) process, is an alternative
process for the extraction and recovery CuSO4·2Cu(OH)2(s) + 2H2SO4 → 3CuSO4(aq) + 4H2O (21)
of copper from an aqueous system. It 3FeS2 + 11.25O2 + 7H2O → (H3O, N, Ag, etc.)Fe3(SO4)2(OH)3 + 4 H2SO4 (22)
involves the use of microorganisms to

2005 July • JOM 49

to 20–25 g/L after washing the leach more efficient mills for fine or ultrafine and removal of elemental sulfur (melting
residue) for feed to the SX-EW plant. grinding of sulfides, and successful and filtration) or pretreating the concen-
Leaching of chalcopyrite concentrate is implementation of autoclave technology trates with a fine grinding (P90 ~25
complete within 10 days. for zinc and refractory gold. µm).
Several acid sulfate pressure leach pro-
The BacTech/Mintek Process Total Pressure Oxidation
cesses were developed for chalcopyrite
Process
BacTech and Mintek, working in concentrates. These included pressure
conjunction with Industrias Penoles SA leaching at two general temperature The total oxidation process uses water
de CV, operated a 2.2 t/d demonstra- regimes: 150°C and 220°C. The former as the leach medium and converts most
tion plant for the bioleaching of copper regime is called partial oxidation with of the sulfide sulfur to copper sulfate and
concentrates in Monterrey, Mexico.13 formation of elemental sulfur and the sulfuric acid.19 Reground concentrate is
Conducted in a series of countercur- latter called total oxidation with complete slurried in acidic recycle solution and
rent reactors, the thermophilic micro- oxidation of the sulfur to sulfate. The pumped into the first compartment of an
organisms are used at temperatures of simple equations are shown by Equations autoclave operated at 210–220°C, with
25–55°C. A pH of 0.5–2.5 is maintained 17, 18, and 19. sparged oxygen to maintain 700 kPa of
within the reactor. Carbon dioxide is In the past ten years, three signifi- overpressure. Basic iron sulfate (hydro-
obtained from ambient air, nutrients are cantly different pressure oxidation leach nium jarosite) is a significant co-product
added to the leach liquor, and retention processes have been developed from which will collect silver (if present) and
time is about 30 days. The technology bench-scale scoping tests and then taken other monovalent cations via the reaction
has also been tested on a wide range of to varying sizes of demonstration plants. shown by Equation 22.
copper concentrates from the Mt. Lyell The developers are Cominco Engineer- Phelps Dodge constructed a concen-
mine in Tasmania, in a small demonstra- ing Services Ltd. (CESL), Dynatec trate leaching demonstration plant in
tion plant over a 15 month period.14 The (formerly a division of Sherritt, Inc.), Baghdad, Arizona to demonstrate the
plant employs moderate thermophiles to Phelps Dodge, and Placer Dome. viability of the total pressure oxidation
oxidize the sulfides followed by conven- process developed by Phelps Dodge and
The CESL Process
tional SX-EW to recover the contained Placer Dome.20 It treats about 136 t/day
copper, which achieved recovery rates The CESL process is a divergent of concentrate to produce about 16,000
of 96.4% and a residency period of six approach to low-severity pressure oxida- t/y of copper cathode via conventional
days. tion in which a high proportion of sulfide SX/EW. After 18 months of continuous
sulfur remains in the elemental form (S0) operation, the Baghdad Concentrate
The BRISA Process
in leach residue.16,17 This process also Leach Plant has demonstrated that the
The fast indirect bioleaching with employs a chloride-enhanced oxidative high-temperature process is suitable for
separate actions (BRISA) process is pressure leach in a controlled amount applications where the dilute acid can
based on bioleaching by the indirect of acid designed to convert the copper be used beneficially.
mechanism. In the BRISA process, the to a basic copper sulfate salt, the iron Recently, Phelps Dodge has started
bioleaching is performed in two separate to hematite, and the sulfur to elemental its development of medium-temperature
biological and chemical stages.15 In the sulfur. The CESL process is composed of pressure leaching in sulfate media
chemical stage, chalcopyrite concen- two leaching stages; the first is a pressure (140–180°C). With its MT-DEW-SX
trates are leached with ferric sulfate at 12 oxidation leach and the leaching residue process,21 chalcopyrite concentrate is
g/L Fe3+ and pH 1.25 in agitated reactors is fed to the second is atmospheric leach, first super-finely ground and then pres-
using silver as a catalyst. High copper mainly via methods shown by Equations sure leached at medium temperature in
extraction (>95 wt.%) is obtained by 20 and 21. an autoclave. After solid-liquid separa-
activating concentrates with 2 mg Ag/g Part of the first leach solution is tion, the leach solution is directly elec-
of concentrate at 70°C and 10 h leach- recycled into the autoclave while the rest trowon to produce copper and the
ing. Silver is then effectively recovered is mixed with the second leach solution electrolyte (with a relative low content
from residues by leaching them with an and fed to SX. After SX, stripping, and of the copper) is either recycled in the
acid-brine medium with 200 g/L of NaCl EW, the process produces high-quality autoclave or mixed with stockpile
and 0.5 M sulfuric acid. copper cathodes. returned leach solution and fed to SX.
The SX raffinate is sent to stockpile leach
PRESSURE SULFATE The Dynatec Process
and the stripped solution is then electro-
LEACHING
The Dynatec process involves oxida- won for final copper cathode produc-
Thermodynamically favorable at an tive leaching of chalcopyrite concentrate tion.
elevated pressure, the use of high pres- at 150°C using coal at a modest dosage
CONCLUSIONS
sure in chalcopyrite concentrate leaching (25 kg/t of concentrate) as an effective
has led to a reliable and cost-competitive anti-agglomerant.18 Sulfide oxidation None of the described processes has
process option. A strong resurgence of chemistry is similar to the CESL process. reached commercial-scale operation.
interest in the pressure sulfate leaching of A high extraction of copper (98+%) is Although each differs in its approach,
chalcopyrite concentrates occurred after achieved by either recycling the unre- leaching copper from chalcopyrite con-
developments in construction materials, acted sulfide to the leach after flotation centrates generally have several prob-

50 JOM • July 2005

lems: the formation of a passivating layer (April 1975). 16. D. Jones, “CESL Copper Process” (Presentation at
on the mineral surfaces during the leach- 5. M.E. Cook and G.E. Atwood, U.S. patent 4,025,400 The Copper Concentrate Treatment Short Course,
(May 1977). held in conjunction with Copper ’99–Cobre ’99,
ing, excess production of sulfuric acid 6. R.F. Dalton et al., “Cuprex—New Chloride-Based Phoenix, AZ, 9–13 October 1999).
or elemental sulfur, purification of leach- Hydrometallurgy to Recover Copper from Sulfide 17. G. McCunn et al., “CESL Process—Moving from
ing solution to control impurities, treat- Ores,” Mining Engineering (January 1988) (reprint). Pilot to Production Scale” (Presentation at the
7. P.R. Kruesi, E.S. Allen, and J.L. Lake, “Cymet International HYDRO–SULFIDES 2004, Santiago,
ment of the insoluble residue for recov- Process—Hydrometallurgical Conversion of Base- Chile, 16–19 August 2004).
ery of precious metals, and stabilization Metal Sulphides to Pure Metals,” CIM Bulletin (June 18. M.J. Collins and D.K. Kofluk, U.S. patent 5,730,776
of the final leaching residue for land- 1973), pp. 81–87. (24 March 1998).
8. J. Moyes, F. Houllis, and R.R. Bhappu, “The Intec 19. J.A. King, D.B. Dreisinger, and D.A. Knight, “The
fill. Copper Process—Demonstration Plant Operating Total Pressure Oxidation of Copper Concentrates”
Despite the problems, leaching copper Experience and Results from the 1999 Campaign” (Presentation at the CIMM District 6 Meeting,
from chalcopyrite concentrates looks (Presentation at The Copper Concentrate Treatment Vancouver, B.C., March 1994).
Short Course, held in conjunction with Copper ’99– 20. J.O. Marsden, R.E. Brewer, and N. Hazen, “Copper
very attractive from environmental, Cobre ’99, Phoenix, AZ, 9–13 October 1999). Concentrate Leaching Developments by Phelps
relatively low grade, or small isolated 9. A.J. Moyes, “The Intec Copper Process—Superior Dodge Corporation,” Hydrometallurgy 2003, Volume
deposit perspectives. Due to these unique and Sustainable Copper Production” (private II—Electrometallurgy and Environmental
communication, April 2002). Hydrometallurgy, ed. C.A. Young et al. (Warrendale, PA:
opportunities, it is likely that a full-scale 10. O. Hyvarinen and M. Hamalainen, U.S. patent TMS, 2003), pp. 1429–1446.
copper leaching-SX-EW plant will be 6,007,600 (December 1999). 21. J.C. Wilmot, R.J. Smith, and R.E. Brewer,
operational within the next five years. 11. Outokumpu, “HydroCopperTM—A Unique and “Concentrate Leach Plant Startup, Operation and
Effective Means of Producing High-Quality Copper Optimization at the Phelps Dodge Bagdad Mine in
Products Directly from Copper Concentrate” (private Arizona,” Pressure Hydrometallurgy 2004, ed. M.J.
References collection, 2005). Collins and V.G. Papangelakis (Montreal, Canada: The
12. W.H. Dresher, “Producing Copper Nature’s Way: Metallurgical Society of CIM, 2004), pp. 77–89.
1. F.P. Haver and M.M. Wong, “Recovery of Copper, Bioleaching,” CND: INNOVATIONS (May 2004), p. 10.
Iron, and Sulfur from Chalcopyrite Concentrate Using 13. P. Miller, “Bioleaching of Copper Concentrates”
a Ferric Chloride Leach,” J. Metals, 23 (2) (1971), pp. (Presentation at The Copper Concentrate Treatment Shijie Wang is senior engineer at Kennecott Utah
25–29. Short Course, held in conjunction with Copper ’99– Copper Corporation.
2. T.A. Phillips, “Economic Evaluation of a Process for Cobre ’99, Phoenix, AZ, 9–13 October 1999).
Ferric Chloride Leaching of Chalcopyrite Concentrate,” 14. A. Potts, “Profitable Bugs,” Mining Magazine, 96 (9) For more information, contact Shijie Wang,
BuMines IC, 8699 (1976), p. 22. (September 2001), pp. 128–134. Kennecott Utah Copper Corporation, 11500 W 2100
3. G.E. Atwood and C.H. Curtis, U.S. patent 3,785,944 15. R. Romero et al., “Copper Recovery from South, P.O. Box 6001, Magna, UT 84044; (801) 569-
(January 1974). Chalcopyrite Concentrates by the BRISA Process,” 6747; (801) 569-6753; e-mail wangs@kennecott.
4. G.E. Atwood and C.H. Curtis, U.S. patent 3,879,272 Hydrometallurgy, 70 (2003), pp. 205–215. com.

In the print version of the journal,

this space presents an
advertisement for
Air Liquide
For more detail about this issue’s
advertisers, review the
table of contents by visiting
http://doc.tms.org/JOM/JOMDepartment