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Abandoned but not forgotten - The recent history of copper hydrometallurgy

Article  in  Metall · January 2006

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 4 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

INTRODUCTION

In the 1960s the copper industry has been undergoing extensive change. The large
copper producing companies in the USA and Canada, for example, Anaconda, Kennecott,
Noranda, and others, have established modern research facilities equipped with up-to-date,
expensive apparatus and staffed with high-calibre metallurgists. One of the research problems
assigned to these laboratories which was given high priority was a study on pollution
abatement in copper production. About that time, it was also realized that chalcopyrite was
the most abundant copper-bearing mineral. Consequently, a great deal of research effort was
directed towards exploring new methods for extracting copper from sulfide concentrates and
in particular from chalcopyrite without polluting the environment.

Research workers attacking this problem immediately found that the literature
available on chalcopyrite was poor; many of the chemical properties of the mineral or the
group of minerals related to chalcopyrite, e.g., bornite, cubanite, etc., were not known. It was
evident, therefore, that the first thing to do was to study the behavior of chalcopyrite towards
different reagents. By acquiring this knowledge, a process may eventually be developed
which efficiently recovers copper from this complex mineral without emitting noxious gases
to the atmosphere, or waste solutions to pollute the streams. As a result, an extensive
literature was generated. Some of this information was published in the international
symposia on hydrometallurgy, the Canadian symposia on hydrometallurgy, sessions devoted
to copper in the AIME national meetings, and the International Symposium on Copper
Extraction and Refining published in 1976, and others.

A number of processes was developed in the twenty-five years period 1970-1995 to

treat copper concentrates by hydrometallurgical route to overcome the pollution problem due
to SO2 emission in smelters. Pilot and commercial scale plants were built and operated for
some time, but eventually all were abandoned few years later (Table 1). Processes developed
only on laboratory scale are not included in this Table. It is constructive to examine why
these processes were abandoned after so much expenditure of effort so that errors should not
be repeated in the future.

TREADWELL PROCESS

Although the action of concentrated H2SO4 on sulfide minerals was known as early as
1893 yet it was only in the 1960s that this reaction received attention because of the fact that
under certain conditions elemental sulfur can be formed and therefore pollution due to SO2 that
generally forms in smelters can be avoided. A process was developed on laboratory scale by
chemical engineers Warren Fuchs, Pete Cadwell, and Edward S. Roberts (1904-1994) of
the Treadwell Corporation in Bronx, New York in 1968 and was tested in Tucson,
Arizona in 1970 under the direction of Francis L. Holdereed director of the Extractive
Metallurgical Research Division of The Anaconda Company. A 100 tonnes chalcopyrite
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 5

concentrate per day pilot plant was constructed for this purpose (Figure 1). Incidentally,
researchers at Kennecott Copper Corporation in Salt Lake City, Utah under the direction of
John D. Prater had a similar process under investigation.

Table 1 – Abandoned hydrometallurgical processes for copper sulfide concentrates

Operating
Process name Plant location Leaching agent
period
1970 Treadwell Tucson, Arizona Concentrated H2SO4
1970 Kennecott Salt Lake City, Utah Concentrated H2SO4
1970-74 Arbiter Anaconda, Montana Ammonia + O2
1971-76 Sherritt-Cominco Fort Saskatchewan, Partial roasting followed
Alberta by dilute H2SO4 leaching
1973 Lurgi-Mitterberg Mühlbach, Austria Dilute sulfuric acid + O2
1976-1983 CLEAR Suharita, Arizona Cupric chloride
1988 CUPREX Madrid, Spain Acid + ferric chloride
1995 Escondida Antofagasta, Chile Ammonia + O2

Figure 1- Francis L.Holdereed (left), Director of Extractive Metallurgical Research Division of The
Anaconda Company in Tucson, Arizona discussing the pilot plant with the superintendent

In the Treadwell process (Figure 2), chalcopyrite concentrate was treated with
concentrated sulfuric acid at 200°C:

CuFeS2 + 4H2SO4 → CuSO4 + FeSO4 + 2SO2 + 2S + 4H2O

 6 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

Concentrated H2SO4 (98%) was selected for the treatment of chalcopyrite because it has the
highest boiling point. As can be seen, copper and iron in the mineral are converted to
water-soluble sulfates, while the sulfur values are converted into elemental sulfur. The
sulfur dioxide formed during the reaction must be converted to sulfuric acid, for recycle.
A number of side reactions may also take place if the conditions are not properly
selected. For example, above 200°C some elemental sulfur will be oxidized to sulfur
dioxide and some of the ferrous sulfate oxidized to ferric sulfate and sulfur dioxide which
represent losses.
Chalcopyrite
concentrate
Conc. H2SO4

Leaching
SO2 to acid plant

Baking
H2O

Leaching

Filtration S + gangue
SO2

Reduction
HCN

Precipitation

Filtration Crystallization
H2

Reduction Decomposition SO2 to acid plant

Copper Fe2O3
Figure 2 – Flowsheet of the Treadwell-Anaconda process for treating chalcopyrite concentrates
with concentrated sulfuric acid

The process was originally carried out using 90% H2SO4 in a continuously
agitated tank indirectly heated by steam. To keep the mixture fluid at all times, a great
excess of acid had to be used. Because of the high affinity of sulfuric acid for water, the
water of reaction was absorbed by the acid and thus sulfur dioxide was the only gaseous
product. Also, because of the high concentration of acid, the solubility of copper and iron
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 7

sulfates was greatly reduced and the salts remained in the solid residue together with the
gangue and elemental sulfur. This facilitated their separation from the excess acid.

However, an economic problem arose, namely a large amount of energy was

required to evaporate spent acid to concentrate it to 90% for recycle. This problem was
solved by using a two-stage process whereby the concentrate was first agitated with a
stoichiometric volume of 98% sulfuric acid. Since no excess of acid was present, the
water of reaction distilled off and the solid to liquid ratio gradually increased until the
reaction mixture solidified. This step was quite short, taking only few minutes. In the
second stage, the solidified mass was heated further until the reaction was complete and
the product then leached with water to remove the soluble sulfates from the gangue and
elemental sulfur.

While Kennecott researchers used a bugging mill for treating the sulfuric acid –
chalcopyrite concentrate, Treadwell used a complicated system of bucket elevator and
silica balls for heat transfer (Figure 3). The process was criticized by many metallurgists
because SO2 was generated and must be converted to acid for recycle and ferrous sulfate
must be decomposed to generate acid for recycle. Further, as a part of the flowsheet, the
solution of sulfates was treated with SO2 to reduce Cu (II) to Cu (I) then precipitating
CuCN selectively with HCN gas. Cuprous cyanide powder was compacted into pellets,
reduced by hydrogen to metallic copper and generating HCN for recycle. Naturally, the
use of HCN was not attractive because of its poisonous nature. It was found also later
that silver contaminates the precipitate. Figure 4 shows equipment in the precipitation
section of the plant.

Figure 3- Treadwell process: a view in the plant

 8 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

The situation was compounded further by the political situation in Chile where the new
socialist regime nationalized the copper industry and Anaconda lost its properties in
Chuquicamata. The Research Department was dissolved, the pilot plant was abandoned,
and the process was dismissed as uneconomical.

Figure 4 – Treadwell process: a view in the precipitation plant

ARBITER PROCESS

The process (Figure 5) was developed in 1970 in a pilot plant at the Extractive
Metallurgical Research Division of The Anaconda Company in Tucson, Arizona under the
direction of Nathaniel Arbiter (Figure 6), a former professor of mineral processing at
Columbia School of Mines in New York City. A commercial 91 tonnes /day copper plant
went in operation at Anaconda, Montana few months later. The leaching plant was composed
of 10 intensely agitated vessels 14 cubic meters each and 5 counter-current decantation
thickeners, with the first overflow filtered to form the pregnant solution. The process is based
on leaching chalcopyrite concentrates with ammonia at 75-80oC in presence of oxygen to
form copper ammine sulfate and iron hydroxide:

2CuFeS2 + 12NH3 + 8½O2 + 2H2O → 2[Cu(NH3)4]2+ + 4NH4+ + 4 SO 24− + Fe2O3

 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 9

After filtering the solids, copper was extracted by LIX-65N, stripped by sulfuric acid, and
electrolyzed to give metallic copper. Lime is then added to the raffinate, and the slurry boiled
to distil ammonia for recovery and precipitate gypsum for disposal:

(NH4)2SO4 + Ca(OH)2 → 2NH3 + CaSO4.2H2O

This ammonia recovery step as well as that from the residue washings proved to be
technically difficult and economically unsound and was the main reason for the shut down.

Chalcopyrite
concentrate
NH3
Air

Leaching

Filtration Solids
CaO
Water

Raffinate
Distillation Solvent Extraction Washing
Water
Organic

Gypsum Washing Filtration Dilute NH3 solution

H2SO4

Stripping Residue
Organic phase
CuSO4 solution

Electrowinning

Copper

Figure 5- Flowsheet of the Arbiter process

Figure 6 - Nathaniel Arbiter

 10 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

SHERRITT-COMINCO PROCESS

In 1971 Sherritt Gordon and Cominco obtained financial support from the Canadian
Government to develop a process for treating copper sulfide concentrates without polluting
the environment. The process was developed and tested in a pilot plant during the period
1971-76 but never applied on commercial scale. It involves partial roasting of chalcopyrite
concentrate then leaching the so-called activated product with dilute sulfuric acid. Hydrogen
sulfide generated during this step is allowed to react with SO2 formed during the partial
roasting to form elemental sulfur. After a series of solution purification, CuSO4 solution is
electrolyzed to get metallic copper. Evidently, the process is so complicated and there are
more obvious and direct routes to get elemental sulfur and copper from chalcopyrite.

LURGI – MITTERBERG PROCESS

This process was developed by Professor Franz Pawlek (1903-1994) (Figure 7) in

1970 and his students at the Technische Hochshule in Berlin and was commercialized by
Lurgi Company in Frankfurt. A small plant was built in 1973 on the mine site in Mitterberg,
a medieval mining town in Tyrol in Austria and operated only for a short time. The process
involves “activation grinding” in a vibration mill of the flotation concentrate to produce a fine
powder of the sulfide minerals with distorted crystalline structure. The material is then
treated at 115oC in an autoclave under oxygen pressure in acid to dissolve copper, precipitate
iron oxide, and liberate elemental sulfur.

Figure 7 – Franz Pawlek (1903-1994)

 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 11

After filtration and washing, the copper sulfate solution is electrolyzed to get metallic
copper and the spent electrolyte recycled to the leaching step. Impurities in solution were
controlled by bleeding a certain volume. There was no provision for solvent extraction of
copper and this may have been the reason why the process did not survive for long although
the exact reason for abandoning the process is not known.

CLEAR PROCESS

The Duval Corporation in Tucson, Arizona was producing 40,000 tons/year copper
from a chalcopyrite concentrate at its Suharita plant in 1976-1983 by a pressure
hydrometallurgical process known as the CEAR Process, an acronym for the process steps:
Copper-Leach-Electrolysis-And-Regeneration (Figure 8). The product is described a “blister
grade copper crystals”. The process was developed under the direction of George Attwood
III (1918-2002) and made use of the valency change of both the copper and iron ions in
solution. At no point in the circuit, an acid was added; however, the solutions were saturated
with sodium and potassium chlorides not only to keep CuCl in solution, but also to increase
the rate of leaching. A mixture of CuCl2 and FeCl3 was used as leaching agent, but the
leaching action was predominantly due to Cu2+ ion. Chalcopyrite is only slightly soluble in
CuCl2 solution even at 120oC but, in presence of excess Cl- ion dissolution readily takes place
because of shifting the reaction to right due to complex formation for both the anodic and
cathodic reactions as follows:

Figure 8 -General view of Duval operations at Suharita plant in Arizona

 12 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

Anodic: CuFeS2 → Cu+ + Fe2+ + 2 S + 3 e-

Cathodic: Cu2+ + e- → Cu+
Cu+ + nCl- → CuCln(n-1)-

The process can be summarized as follows (Figure.9):

Chalcopyrite
CuCl2, FeCl2
NaCl + KCl
st
Leaching 1 stage

Solution
Filtration
CuC12, FeC13
O2
Leaching 2nd stage Electrolysis

H2 O
Filtration Washing

Residue Melting, Casting

S, FeOOH,
jarosite, gangue
Electrorefining Ag

Cu

Figure 9 -Simplified flowsheet of the CLEAR process

First stage leaching

In this stage the molar ratio Cu2+/Fe3+ in the leach solution is about 5, and only one
half of the chalcopyrite is dissolved according to the following reactions:

CuFeS2 + 3 CuCl2 → 4 CuCl + FeCl2 + 2 S

CuFeS2 + 3 FeCl3 → CuCl + 4 FeCl2 + 2 S

The molar ratio Cl-/CuCl necessary to keep CuCl in solution and to yield reasonable reaction
rate is about 20. The chloride ion is added as NaCl and KCl. Leaching is conducted at 105-
110oC in a horizontal autoclave made of fibreglass (Figure 10). The autoclave is 30 m long
and about 5 m diameter, divided into 10 compartments each fitted with a powerful turbine
agitator. The autoclave is not insulated; the heat lost by radiation is compensated by that
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 13

generated during the reaction. Copper in solution leaving the autoclave is mainly in the
cuprous state. Use is made of this fact in the subsequent electrowinning step. That is why
the solutions are handled carefully without excessive exposure to the air to avoid oxidation.
Also, after cooling to 80oC and settling in closed thickeners, some cement copper is added
with continuous agitation to reduce the remaining cupric ion:

Cu2+ + Cu →2 Cu+

The solution is then sent to the electrolytic cells for copper recovery, while the residue is sent
to the second stage leaching.

Second stage leaching

In this stage the remaining unreacted chalcopyrite is leached in presence of oxygen at

600 kPa, and 135-140oC for 90 minutes in a titanium autoclave. The leach solution is spent
electrolyte in which the molar ration Cu2+/Fe3+ is 10 (as compared to 5 in the first stage). In
addition, a great part of the iron however, is in the ferrous state. Although the excess chloride
ion is not needed as a complexing agent, nevertheless, the solution is saturated with NaCl and
KCl, since these are recycle solutions. In this stage, not only chalcopyrite is solubilized as in
the first stage, but also both the ferrous and the cuprous ions are oxidized further due to the
presence of oxygen:

2 Fe2+ + 2 H+ + ½O2 →2 Fe3+ + H2O

2 Cu+ + 2 H+ + ½ O2 →2 Cu2+ + H2O

Although no acid is added in the system, the hydrolysis and precipitation of ferric ion
furnishes the acid necessary for oxidation:

2 Fe3+ + 4 H2O →2 FeOOH + 6 H+

Thus, the overall reaction that takes place is:

2 Fe2+ + 4 Cu+ + 1½ O2 + H2O →2 FeOOH + 4 Cu2+

It is not essential to precipitate all the ferric ion since the solutions will be recycled to the first
stage later. However, due to the oxidation of some of the elemental sulfur, a minor amount of
sulfate ions are present in solution. This leads to the precipitation of some basic iron sulfate
in the form of potassium jarosite:

3 Fe3+ + 2 SO 24− + K+ + 6 OH- → KFe3(SO4)2(OH)6

 14 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

which is suitable as a soil conditioner. It contains 20-25% S in the elemental form and <
0.5% Cu as chalcopyrite.

Figure 10- Fiberglass autoclave 50 meters long designed for mild leaching conditions, fabricated by
Sundt Fiberglass in Tucson, Arizona

Electrolysis

Copper is recovered from the first stage leach solution by electrolysis in a specially
designed diaphragm cells, using a copper cathode and a graphite anode. Copper is deposited
in form of large dendrides which is scraped continuously by mechanical conveyers from the
bottom of the cell. The reactions taking place are the following (ignoring the complexing Cl-
ion):
Cathodic: Cu+ + e- →Cu
Anodic Cu+ →Cu2+ + e-
Overall reaction: 2 Cu+ →Cu + Cu2+

It can be seen that only half of the copper is precipitated while the other half is recycled as a
leaching agent in form of CuCl2. About 10% of the ferrous ion is oxidized to ferric at the
anode. A small amount of chlorine is also evolved. Copper produced by this process is
99.9+%, but still not suitable for the market because it contains about 24 ppm silver (also
about 100 ppm Fe). No method was found to remove silver from the solution before the
electrolytic step.

Refining

The product is described a “blister grade copper crystals” (Figure 11). As a result of
the presence of silver in the product the copper powder is melted and cast in form of anodes
for electrorefining to recover the silver and have a product acceptable for the market.
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 15

Figure 11- Copper product of CLEAR process known as “blister grade copper crystals”

Remarks

For each tonne copper produced, 9 tonnes of salt (KCl + NaCl) are in continuous
circulation. The effort done to keep copper in solution in the cuprous form is not after all
exploited in the electrowinning step, because only half of the copper is precipitated in the
elemental form and the other half is oxidized to the cupric state, i.e., the recovery step is
essentially a disproportionation reaction:

2 Cu+ ' Cu + Cu2+

which may be conducted more efficiently and possibly at a lower cost using other methods if
at all necessary since in this case cementation with metallic iron followed by oxhydrolysis of
ferrous chloride solution may be a better suggestion.

CUPREX PROCESS

The CUPREX process was developed in 1988 as a joint venture between Tecnicas Reunidas
in Spain, ICI in United Kingdom, and Nerco Minerals. It uses ICI's selective DS 5443
extractant and Tecnicas Reunidas' Metchlor electrowinning cell. Several two-to three-week
runs on a variety of copper concentrates were completed at Tecnicas Reunidas's facilities in
Madrid, and the process was considered ready for commercialization. The advantage of this
new extractant is that it permits the recovery of copper from chloride medium without the
necessity to transfer from chloride to sulfate.
In this process, copper concentrate is leached in two stages with ferric chloride solution at
95°C and atmospheric pressure to produce a solution of cupric chloride, ferrous chloride, and
elemental sulfur:
 16 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

CuFeS2 + 4Fe3+ → Cu2+ + 5Fe2+ + 2S

The leach residue consists of gangue, pyrite and sulfur. The pregnant solution, is sent to the
solvent extraction circuit where it is contacted with a kerosene solution of DS 5443. Using
three extraction stages, copper in the aqueous phase is reduced to less than 0.5 g/L.

The loaded organic is scrubbed with spent anolyte from the electrowinning cell and
then stripped by contacting with water at 65°C. Three strip stages produce an aqueous copper
chloride solution grading over 90 g/L Cu. The chloride ion content is then increased by
adding sodium chloride, which enhances conductivity and minimizes the possibility of the
precipitation of cuprous chloride, and the solution is sent to the Metchlor electrolysis cell.
The cell has two compartments separated by a cation exchange membrane. It uses a titanium
cathode and an inert anode. Copper granules are deposited in the cathode compartment, and
the electronic balance in the catholyte is maintained by transfer of sodium ions from the
anolyte through the membrane.

Spent catholyte leaving the cell is a sodium chloride solution containing about 10 g/L
Cu roughly divided between the cupric and cuprous oxidation states. This proceeds to the
reforming stage where it is treated with chlorine gas from the anode compartment of the
electrowinning cell to oxidize the cuprous ions to cupric. Cupric chloride is removed from the
reformed catholyte in the depletion section by contacting it with copper-free organic from the
stripping section of the solvent extraction. A two-stage depletion at a high 8:1
organic/aqueous ratio reduces copper in the spent catholyte to less than 0.1 g/L. The organic,
containing relatively little copper, is recycled to the extraction unit and the aqueous raffinate
becomes anolyte in the electrowinning cell.

Any silver in the original concentrate reports in the raffinate from the solvent
extraction stage and can be recovered by zinc dust precipitation. Excess iron from the
leaching of chalcopyrite is removed as goethite in a subsequent pressure oxidation step which
simultaneously regenerates part of the leachant. The remaining ferric chloride leachant is
regenerated by chlorine from the electrowinning cell.

ESCONDIDA PROCESS

The Escondida process was developed by Wilem Duyvesteyn and coworkers at the
Minerals Laboratory of BHP in Sunnyvale, California in 1991 for the treatment of copper
concentrates from Escondida mine in northern Chile, and was closed few years later. The
600 kg/day plant was constructed at Coloso near Antofagasta in Chile. The ore was mainly
chalcocite, Cu2S, and it was intended to extract only half of the copper to produce a CuS
concentrate for shipment (Figure 12).
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 17

Chalcocite
concentrate
NH3
Air

Leaching

Filtration Solids
Water

Solvent Extraction Washing

Water
Organic

Dilute NH3 solution Washing Filtration Dilute NH3 solution

H2SO4

Stripping Flotation Gangue + Pyrite

Organic phase
CuSO4 solution

Electrowinning CuS concentrate

Copper
Figure 12- Simlified flowsheet of Escondida process

An ammoniacal solution under mildly oxidizing conditions at atmospheric pressure

was used to leach half of the copper in the concentrate. The mild leaching conditions also
prevent the dissolution of unwanted impurities. Solution purification is carried out by solvent
extraction with LIX-54 which is selective for copper ions. Stripping is conducted by sulfuric
acid. Copper cathodes of high purity were produced in a conventional sulfuric acid-based
electrowinning system. Ammonia was regenerated from the solutions by distillation and
recycled for leaching. One scrubbing step was needed between the ammoniacal and acid
circuits. The residue is a high-grade copper concentrate ready for shipment.

Chalcocite behaves in leaching as if it were a mixture of metallic copper and cupric

sulfide:

Cu2S ≈ Cu + CuS
Cu + 4 NH3 + ½ O2 + H2O → [Cu(NH3)4]2+ + 2 OH-

Conditions were so chosen that CuS was not attacked. The reaction is slow but accelerated
when NH +4 ion is present. There are some problems, however, with ammonia leaching:
 18 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1)

• Absorbing CO2 from the atmosphere. Thus an appreciable amount of ammonium ion
builds up
• Partial oxidation of NH3 to nitrite, Cu2+ ion acting as catalyst:

2 NH3(aq) + 3 O2 + 2 OH- → 2 NO −2 + 4 H2O

• Transferring the extraction system from ammoniacal to acid generates a dilute

ammoniacal solution which necessitates recovery
• Washing of residue also generates a similar solution

Recovery of NH3 from such solutions requires boiling with lime to distill off NH3 and form
calcium carbonate for disposal. If some sulfides go in solution, then a corresponding amount
of gypsum will also form for disposal. Recovery of ammonia from ammonium salts is not
economical and losses of ammonia cannot be tolerated.

EPILOGUE

ƒ Chalcopyrite, the major copper mineral, is roughly one third copper, one third iron, and one
third sulfur. Any attempt to recover copper must take into consideration the other two
components
ƒ Elemental sulfur and iron oxide are the two preferred products when leaching chalcopyrite
concentrates
ƒ Attempts to use oxidizing agents other than oxygen are futile
ƒ Ammonia is only suitable as a leaching agent for sulfides when ammonium sulfate is
recovered and marketed as a fertilizer
ƒ The chloride system has advantages in leaching but has problems in the recovery section

SUGGESTED READINGS

1. N. Arbiter and A.W. Fletcher, “Copper Hydrometallurgy. Evolution and

Milestones”, Mining Engineering 118-123 (1994) February
2. S. Biangardi and H. Pietsch, “The Treatment of Sulfidic Copper Ores by the Lurgi-
Mitterberg Process”, pp. 5.1-5.7 in Int. Chem. Eng. Symposium Series No. 42 (1975)
3. R.F. Dalton et al., “Cuprex Metal Extraction Process”, J. Metals 43, 51-56
(1991)
4. F. P. Dewey, “The sulfuric Acid Process of Treating Lixiviation Sulfides”,
Trans. AIME 26, 242-263 (1896), U. S. Patents 490 068 (1893) and 561 571
(1896)
5. W. Fuchs, “Extraction of Sulfide Ores with Hot Concentrated Sulfuric Acid”.
German Patent, 1 815 513 (1969), Canadian Patent 964 455 (1971)
 THE JOHN E. DUTRIZAC SYMPOSIUM ON COPPER HYDROMETALLURGY (BOOK 1) 19

6. F. Habashi, Readings in Historical Metallurgy. Volume 1 – Changing

Technology in Extractive Metallurgy, Métallurgie Extractive Québec, Quebec
City 2006. Distributed by Laval University Bookstore “Zone
7. F. Habashi, A Textbook of Hydrometallurgy, Métallurgie Extractive Québec, Sainte-
Foy, Québec 1993, second edition 1999, Métallurgie Extractive Québec, Quebec City
2006. Distributed by Laval University Bookstore “Zone”
8. F. Habashi, Chalcopyrite. Its Chemistry and Metallurgy, McGraw-Hill International,
New York 1978
9. F. Habashi and R. Dugdale, “The Action of Concentrated Sulfuric Acid on
Chalcopyrite”, Erzmetall 65 (6), 269-273 (1974)
10. J. D. Prater, P. B. Queneau, and T. J. Hudson, « Sulfation of Copper-Iron
Sulfides with Concentrated Sulfuric Acid”, J. Metals 22 (12), 23-7 (1970)
11. F.W. Schweitzer and R.W. Livingston, “Duval’s CLEAR Hydrometallurgical
Process”, pp. 221-227 in Chloride Electrometallurgy, edited by Peter D. Parker, The
Metallurgical Society of AIME, New York City 1982
12. G.M. Swinkels et al., “The Sherritt-Cominco Copper Process”, in 3 parts, CIM
Bulletin 71, 790-825(1978) February

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