Copper 1

Copper
Adalbert Lossin, Norddeutsche Affinerie Aktiengesellschaft, Hamburg, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 2 5.7. Continuous Matte Conversion . . . . 35

2. Physical Properties . . . . . . . . . . . 4 5.7.1. Noranda Process . . . . . . . . . . . . . 35
3. Chemical Properties . . . . . . . . . . 6 5.7.2. Mitsubishi Process . . . . . . . . . . . . 36
4. Occurrence . . . . . . . . . . . . . . . . 8 5.7.3. Kennecott/Outokumpu Flash Convert-
4.1. Copper Minerals . . . . . . . . . . . . 8 ing Process . . . . . . . . . . . . . . . . . 38
4.2. Origin of Copper Ores . . . . . . . . . 9 5.8. Direct Blister Smelting . . . . . . . . 38
4.3. Copper Ore Deposits . . . . . . . . . . 10 5.8.1. Blister Flash Smelting . . . . . . . . . 38
4.4. Copper Resources . . . . . . . . . . . . 10 5.8.2. QS Process . . . . . . . . . . . . . . . . . 39
4.5. Mining . . . . . . . . . . . . . . . . . . . 10 5.9. Copper Recycling . . . . . . . . . . . . 39
5. Production . . . . . . . . . . . . . . . . 11 5.10. Hydrometallurgical Extraction . . . 40
5.1. Beneficiation . . . . . . . . . . . . . . . 12 6. Refining . . . . . . . . . . . . . . . . . . 45
5.2. Roasting . . . . . . . . . . . . . . . . . . 15 6.1. Pyrometallurgical Refining . . . . . . 45
5.3. Pyrometallurgical Principles . . . . . 17 6.1.1. Discontinuous Fire Refining . . . . . . 45
5.3.1. Behavior of the Components . . . . . . 17 6.1.2. Continuous Fire Refining . . . . . . . . 46
5.3.2. Matte . . . . . . . . . . . . . . . . . . . . 17 6.1.3. Casting of Anodes . . . . . . . . . . . . 46
5.3.3. Slags . . . . . . . . . . . . . . . . . . . . . 17 6.2. Electrolytic Refining . . . . . . . . . . 47
5.3.4. Oxidizing Smelting Processes . . . . . 19 6.2.1. Principles . . . . . . . . . . . . . . . . . . 47
5.3.5. Proposals . . . . . . . . . . . . . . . . . . 19 6.2.2. Practice of Electrorefining . . . . . . . 49
5.4. Traditional Bath Smelting . . . . . . 21 6.3. Melting and Casting . . . . . . . . . . 50
5.4.1. Blast Furnace Smelting . . . . . . . . . 21 6.3.1. Remelting of Cathodes . . . . . . . . . 51
5.4.2. Reverberatory Furnace Smelting . . . 22 6.3.2. Discontinuous Casting . . . . . . . . . . 51
5.4.3. Electric Furnace Smelting . . . . . . . 22 6.3.3. Continuous Casting . . . . . . . . . . . 51
5.4.4. Isasmelt Furnace . . . . . . . . . . . . . 24 6.3.4. Continuous Rod Casting and Rolling 51
5.4.5. Noranda Process . . . . . . . . . . . . . 24 6.4. Copper Powder . . . . . . . . . . . . . 52
5.4.6. CMT/Teniente Process . . . . . . . . . 25 6.5. Copper Grades and Standardization 53
5.4.7. Vanyukov Process . . . . . . . . . . . . 25 6.6. Quality Control and Analysis . . . . 54
5.4.8. Baiyin Process . . . . . . . . . . . . . . 26 7. Processing and Uses . . . . . . . . . . 55
5.5. Autogenous Smelting . . . . . . . . . . 26 7.1. Working Processes . . . . . . . . . . . 55
5.5.1. Outokumpu Flash Smelting . . . . . . 27 7.2. Other Fabricating Methods . . . . . 56
5.5.2. Inco Flash Smelting . . . . . . . . . . . 29 7.3. Uses . . . . . . . . . . . . . . . . . . . . . 57
5.5.3. KIVCET Cyclone Smelting . . . . . . 30 8. Economic Aspects . . . . . . . . . . . . 58
5.5.4. Contop Matte Smelting . . . . . . . . . 30 9. Environmental Protection . . . . . . 60
5.5.5. Flame Cyclone Smelting . . . . . . . . 31 10. Toxicology . . . . . . . . . . . . . . . . . 61
5.6. Discontinuous Matte Conversion . . 32 11. References . . . . . . . . . . . . . . . . . 62

1. Introduction silver), its outstanding ductility and thus excel-

Copper [7440-50-8], the red metal, apart from
gold the only metallic element with a color dif-
ferent from a gray tone, has been known since the
early days of the human race. It has always been
one of the significant materials, and today it is the
most frequently used heavy nonferrous metal.
The utility of pure copper is based on its physi-
cal and chemical properties, above all, its electri-
cal and thermal conductivity (exceeded only by
lent workability, and its corrosion resistance (a
chemical behavior making it a half-noble metal).
Its common alloys, particularly brass and
bronze, are of great practical importance
(→ Copper Alloys). Copper compounds and
ores are distinguished by bright coloration, espe-
cially reds, greens, and blues (→ Copper Com-
pounds). Copper in soil is an essential trace ele-
ment for most creatures, including humans.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a07 471
2 Copper
Etymology. According to mythology, the
goddess Venus (or Aphrodite) was born on
the Mediterranean island of Cyprus, formerly
Kypros (Greek), where copper was exploited
millennia before Christ. Therefore, in early
times the Romans named it cyprium, later called
cuprum. This name is the origin of copper and of
the corresponding words in most Romance and
Germanic languages, e.g., cobre (Spanish and
Portuguese), cuivre (French), Kupfer (German),
koper (Dutch), and koppar (Swedish).
History [21–24]. The first metals found by
Neolithic man were gold and copper, later sil-
ver and meteoric iron. The earliest findings of
copper are presumed to be nearly nine millen-
nia old and came from the region near Konya in
southern Anatolia (Turkey). Until recently the
six-millennia-old copper implements from Iran
(Tepe Sialk) were presumed to be the oldest. In
the Old World, copper has been worked and used
since approximately
7000 b.c. Anatolia
4000 b.c. Egypt, Mesopotamia, Palestine, Iran,
and Turkestan
3000 b.c. Aegean, India
2600 b.c. Cyprus
2500 b.c. Iberia, Transcaucasia, and China
2200 b.c. Central Europe
2000 b.c. British Isles
1500 b.c. Scandinavia
Empirical experience over millennia has led
to an astonishing knowledge of copper metallur-
gical operations:
1) Native copper was hardened by hammering
(cold working) and softened by moderate
heating (annealing).
2) Heating to higher temperatures (charcoal and
bellows) produced molten copper and made
possible the founding into forms of stone,
clay, and later metal.
3) Similar treatment of the conspicuously col-
ored oxidized copper ores formed copper
metal.
4) The same treatment of sulfide copper ores
(chalcopyrite), however, did not result in cop-
per metal, but in copper matte (a sulfidic in-
termediate). Not before 2000 b.c. did people
succeed in converting the matte into copper
by repeated roasting and smelting.
5) In early times, bronze (copper – tin alloy) was
won from complex ores, the Bronze Age be-
ginning ca. 2800 b.c. At first, copper ores
were smelted with tin ores; later, bronze was
produced from metallic copper and tin. Brass
(copper – zinc alloy) was known ca. 1000 b.c.
and became widely used in the era of the Ro-
man Empire.
In Roman times, most copper ore was mined
in Spain (Rio Tinto) and Cyprus. With the fall of
the Roman Empire, mining in Europe came to a
virtual halt. In Germany (Saxony), mining activ-
ities were not resumed until 920 a.d. During the
Middle Ages, mining and winning of metals ex-
panded from Germany over the rest of Europe.
In the middle of the 16th century, the current
knowledge of metals was compiled in a detailed
publication [23] by Georgius Agricola, De
Re Metallica (1556).
Independent of the Old World, the Indians of
North America had formed utensils by working
native copper long before the time of Christ, al-
though the skills of smelting and casting were
unknown to them. On the other hand, the skill of
copper casting was known in Peru ca. 500 a.d.,
and in the 15th century the Incas knew how to
win the metal from sulfide ores.
Around 1500, Germany was the world leader
in copper production, and the Fugger family
dominated world copper trade. By 1800, Eng-
land had gained first place, processing ores from
her own sources and foreign pits into metal. Near
1850, Chile became the most important producer
of copper ores, and toward the end of the last
century, the United States had taken the world
lead in mining copper ores and in production of
refined copper.
Technical development in the copper indus-
try has made enormous progress in the last 120
years. The blast furnace, based on the oldest
principle of copper production, was continually
developed into more efficient units. Neverthe-
less, after World War I, it was increasingly re-
placed by the reverberatory furnace, first con-
structed in the United States. Since the end of
World War II, this furnace has been superseded
slowly by the flash smelting furnace invented
in Finland. Recently, several even more mod-
ern methods, especially from Canada and Japan,
have begun to compete with the older processes.
An important development in producing
crude metal was the application of the Besse-
mer converter concept to copper metallurgy by
 Copper 3

Manhès and David (France, 1880): this prin- 2) High dependence on defects, e.g., electrical
ciple is still the most widely used method for and thermal conductivity, plastic behavior,
copper converting in the world. kinetic phenomena, and resistance to corro-
Over time the requirements for copper pu- sion
rity have become increasingly stringent. The in-
vention and development of electrolysis by J. B. The variations in properties are caused ei-
Elkington (England, 1865) and E. Wohlwill ther by physical lattice imperfections (disloca-
(Germany, 1876) made refining of high-purity tions, lattice voids, and interstitial atoms) or by
copper possible. chemical imperfections (substitutional solid so-
In addition, the quantity of copper produced lutions).
has increased immensely (Table 1). Since 1800,
ca. 375 × 106 t of primary copper has been Atomic and Nuclear Properties. The
mined in the world, but of this only ca. 10 × 106 t atomic number of copper is 29, and the atomic
was mined between 1800 and 1900. mass Ar is 63.546 ± 0.003 (IUPAC, 1983).
Copper consists of two natural isotopes, 63 Cu
Table 1. World mine production of copper (approximate, from sev-
eral sources) (68.94 %) and 65 Cu (31.06 %). There are also
nine synthetic radioactive isotopes with atomic
Production, 103 t Production, 103 t
Year Year
masses between 58 and 68, of which 67 Cu has
1700 9 1970 6400 the longest half-life, ca. 58.5 h.
1800 17 1975 7300
1850 57 1980 7900
1900 450 1985 8300 Crystal Structure. At moderate pressures,
1950 2500 1990 9225 copper crystallizes from low temperatures up to
1955 3100 1995 10 050
1960 4200 1997 11 525 its melting point in a cubic closest-packed (ccp)
1965 5000 lattice, type A 1 (also F1 or Cu) with the co-
ordination number 12. X-ray structure analysis
yields the following dimensions (at 20 ◦ C):
Lattice constant 0.36152 nm
2. Physical Properties Minimum interatomic distance 0.2551 nm
Atomic radius 0.1276 nm
Most properties of copper metal depend on the Atomic volume 7.114 cm3 /mol
degree of purity and on the source of the metal.
Variations in properties are caused by There is also a high-pressure modification,
1) Grade of copper, i.e., the oxygen con- which forms at ca. 400 MPa and 100 ◦ C.
tent: tough-pitch copper, deoxidized copper,
oxygen-free copper Density. The theoretical density at 20 ◦ C,
2) Content of native impurities (e.g., arsenic, computed from lattice constant and atomic mass
bismuth) or remnants of additives (e.g., phos- is 8.93 g/cm3 . The international standard was
phorus), which form solid solutions or sepa- fixed at 8.89 g/cm3 in 1913 by the IEC (Interna-
rate phases at the grain boundaries tional Electrotechnical Commission). The max-
3) Thermal and mechanical pretreatment of the imum value for 99.999 % copper reaches nearly
metal, which lead to states such as cast cop- 8.96 g/cm3 .
per, hot-rolled copper, cold-worked (hard) The density of commercial copper depends
copper, annealed (soft) copper, and sintered on its composition, especially the oxygen con-
copper tent, its mechanical and thermal pretreatment,
and the temperature. At 20 ◦ C, a wide range of
These property differences are caused by the values are found:
defects in the crystal lattice. Two groups of prop-
Cold-worked and annealed copper 8.89 – 8.93 g/cm3
erties are to be distinguished: Cast tough-pitch electrolytic copper 8.30 – 8.70 g/cm3
1) Low dependence on crystal lattice defects, Cast oxygen-free electrolytic copper 8.85 – 8.93 g/cm3
e.g., caloric and thermodynamic properties,
magnetic behavior, and nuclear characteris-
tics
4 Copper

The values for cold-worked copper are higher copper is a high-strength material without cold
than those of castings because the castings have brittleness.
pores and gas cavities. The changes in typical mechanical properties
The density of copper is nearly a linear func- such as tensile strength, elongation, and hard-
tion of temperature, with a discontinuity at the ness by heat treatment result from recrystalliza-
melting point: tion [25]. The dependence of recrystallization
temperature and grain size on the duration of
Temperature, ◦ C Density, g/cm3 heating, the amount of previous cold deforma-
tion, and the degree of purity of copper can be
solid copper
20 8.93 determined from diagrams. The recrystallization
600 8.68 temperature is ca. 140 ◦ C for high-purity copper
900
1 083
8.47
8.32
and is 200 – 300 ◦ C for common types of copper.
liquid copper A low recrystallization temperature is usually
1 083 7.99 advantageous, but higher values are required to
1 200 7.81
maintain strength and hardness if the metal is
heated during use.
The solidification shrinkage is 4 %; the spe-
cific volume at 20 ◦ C is 0.112 cm3 /g. Thermal Properties. Important thermal val-
ues are compiled in Table 3. The thermal con-
Mechanical Properties. Important mechan- ductivity of copper is the highest of all metals
ical values are given in Table 2. High-purity cop- except silver.
per is an extremely ductile metal. Cold working
increases the hardness and tensile strength (hard Table 3. Thermal properties of copper
or hard-worked copper); subsequent annealing Property Unit Value
eliminates the hardening and strengthening so
that the original soft state can be reproduced (soft Melting point K 1356 (1083 ◦ C)
Boiling point K 2868 (2595 ◦ C)
copper). The working processes are based on Heat of fusion J/g 210
this behavior (Section 7.1). Impurities that form Heat of vaporization J/g 4810
Vapor pressure (at mp) Pa 0.073
solid solutions of the substitutional type likewise Specific heat capacity
increase hardness and tensile strength. at 293 K (20 ◦ C)
and 100 kPa (1 bar) J g−1 K−1 0.385
Table 2. Mechanical properties of copper at room temperature at 1230 K (957 ◦ C)
and 100 kPa 0.494
Property Unit Anealed Cold-worked Average specific heat
(soft) copper (hard) copper 273 – 573 K (0 – 300 ◦ C)
at 100 kPa (1 bar) J g−1 K−1 0.411
Elastic modulus GPa 100 – 120 120 – 130 273 – 1273 K (0 – 1000 ◦ C)
Shearing modulus GPa 40 – 45 45 – 50 at 100 kPa 0.437
Poisson’s ratio 0.35 Coefficient of linear thermal
Tensile strength MPa 200 – 250 300 – 360 expansion
Yield strength MPa 40 – 120 250 – 320 273 – 373 K (0 – 100 ◦ C) K−1 16.9 × 10−6
Elongation % 30 – 40 3–5 273 – 673 K (0 – 400 ◦ C) 17.9 × 10−6
Brinell hardness (HB) 40 – 50 80 – 110 between 273 and 1173 K
Vickers hardness (HV) 45 – 55 90 – 120 (0 – 900 ◦ C) 19.8 × 10−6
Scratch hardness ≈3 Thermal conductivity
at 293 K (20 ◦ C) W m−1 K−1 394
Pure copper has outstanding hot workability
without hot brittleness, but the high-temperature
strength is low. Detrimental impurities, those Electrical Properties. In practice, the most
that decrease the strength at high temperatures, important property of copper is its high elec-
are principally lead, bismuth, antimony, sele- trical conductivity; among all metals only sil-
nium, tellurium, and sulfur. The concentration ver is a better conductor. Both electrical con-
of oxides of such elements at the grain bound- ductivity and thermal conductivity are con-
aries during heating causes the embrittlement. nected with the Wiedemann – Franz relation and
However, such an effect can be desirable when show strong dependence on temperature (Ta-
free cutting is required. At subzero temperatures, ble 4). The old American standard, 100 %
 Copper 5

IACS (International Annealed Copper Stan- The surface tension of molten copper is
dard), corresponds to 58.0 MS/m at 20 ◦ C, and 11.25 × 10−3 N/cm at 1150 ◦ C, and the dynamic
it is still widely used in the United States. viscosity is 3.5 × 10−3 Pa · s at 1100 ◦ C.
The corresponding electrical resistivity (
) is Detailed physical-property information and
1.7241×10−8 Ω · cm, and the less usual resistiv- data are to be found in the literature, particularly
ity based on weight (density of 8.89 g/cm3 , IEC) as tabular compilations [25–30].
is 0.1533 Ω g m−1 . The corresponding temper-
ature coefficients are 0.0068 ×10−8 Ω m K−1
(d
/dT ) and 0.00393 K−1 (
−1 d
/dT ). The 3. Chemical Properties
theoretical conductivity at 20 ◦ C is nearly
60.0 MS/m or 103.4 % IACS, and today com- In the Periodic Table copper is placed in the
mercial oxygen-free copper (e.g., Cu-OF) has a first transition series (period 4). It belongs to
conductivity of 101 % IACS. Group 11 and, together with silver and gold,
Table 4. Temperature dependence of thermal and electrical conduc- forms the coinage metals. Its electron config-
tivity of copper uration is [Ar] 3d 10 4s1 . Copper compounds are
Temperature Thermal Electrical known in oxidation states ranging from +1 to +4,
conductivity, conductivity, although the +2 (cupric) and the +1 (cuprous) are
W m−1 K MS/m
by far the most common. In aqueous solutions
K ◦
C or below 800 ◦ C, the +2 oxidation state is the
most stable.
17 −256 5 000
73 −200 574 460 Copper(I) compounds such as CuCl and CuI
113 −160 450 are diamagnetic colorless materials, except for
173 −100 435 110
273 0 398 60
those whose color results from charge-transfer
293 20 394 58 bands, for example, Cu2 O. Cu+ ions, [Ar] 3d 10 ,
373 100 385 44 are coordinated in a linear (two ligands) or tetra-
473 200 381 34
573 300 377 27 hedral fashion (four ligands).
973 700 338 15 Copper(II) compounds such as CuSO4
· 5 H2 O are paramagnetic blue or green sub-
The factors that increase the strength de- stances, the color of which results from strong
crease electrical conductivity: cold working and absorption bands in the region between 600 and
elements that form solid solutions. Elements 900 nm caused by d – d electron transfer pro-
that form oxidic compounds that separate at cesses. The Cu2+ ion is a d 9 system and gener-
grain boundaries affect electrical properties only ally sixfold coordinated in a distorted octahedral
slightly. Copper may lose up to ca. 3 % of its con- manner.
ductivity by cold working; however, subsequent Copper(III) compounds are mostly diamag-
annealing restores the original value. There is a netic. Cuprates like NaCuO2 can be obtained
simple rule: the harder the copper, the lower is by heating the oxides in pure oxygen. In chem-
its conductivity. istry only a few Cu3+ complexes are known, but
it appears that Cu3+ plays an important role in
Other Properties. High-purity copper is biochemistry, especially with deprotonated pep-
diamagnetic with a mass susceptibility of tides.
− 0.085 × 10−6 cm3 /g at room temperature. Copper(IV) compounds are not well known
The dependence on temperature is small. How- except for Cs2 [CuF6 ].
ever, a very low content of iron can strongly af-
fect the magnetic properties of copper. Behavior in Air. Copper in dry air at room
The lower the frequency of light, the higher temperature slowly develops a thin protective
the reflectivity of copper. The color of a clean, film of copper(I) oxide [1317-39-1]. On heating
solid surface of high-purity copper is typically to a high temperature in the presence of oxygen,
salmon red. copper forms first copper(I) oxide, then cop-
per(II) oxide [1317-38-0], both of which cover
the metal as a loose scale.
6 Copper
In the atmosphere, the surface of copper oxi-
dizes in the course of years to a mixture of green
basic salts, the patina, which consists chiefly
of the basic sulfate, with some basic carbonate.
(In a marine atmosphere, there is also some ba-
sic chloride.) Such covering layers protect the
metal.
Behavior versus Diverse Substances.
While many substances scarcely react with
copper under dry conditions, the rate of at-
tack increases considerably in the presence of
moisture. Copper has a high affinity for free
halogens, molten sulfur or hydrogen sulfide.
Standard electron potentials of copper are as
follows [31], [32]:
Potentials in standard (acid) solution:
Cu+ + e− −→ Cu E 0 = 0.521 V
Cu2+ + 2 e− −→ Cu E 0 = 0.153 V
Potentials with complexing ligands:
[Cu(NH3 )4 ]2+ + 2 e− −→ Cu + 4 NH3 E 0 = − 0.11 V
[Cu(CN)2 ]− + e− −→ Cu + 2 CN− E 0 = − 0.43 V
As the standard electron potentials show, copper
metal is stable to nonoxidizing acids like dilute
sulfuric or hydrochloric acid, similar to the pre-
cious metals. Dissolution of copper is possible
in oxidizing acids such as nitric acid or hot con-
centrated sulfuric acid. Also other redox systems
such as iron(III) or copper(II) chloride solutions
are suitable reagents for leaching copper in prac-
tice.
Copper dissolves not only in oxidizing acids
but also, for example, in ammonia or cyanide so-
lutions in the presence of oxygen because stable
complexes are formed. Also acetic acid together
with oxygen or hydrogen peroxide attacks cop-
per forming a green pigment called verdigris.
Free Cu+ ions are not stable in aqueous solu-
tion although Cu+ (3d 10 ) has a filled d shell.
Spontaneous disproportion into Cu2+ and Cu
takes place.
2 Cu+ −→ Cu2+ + Cu E 0 = 0.37 V
K = [Cu2+ ]/[Cu+ ] = 106
The distorted octahedral coordination of six wa-
ter molecules around the Cu2+ ion (d 9 ) gives
an additional stabilization energy (ligand-field
effect). In aqueous solutions, Cu+ is only ex-
istent in form of very stable complexes like
[Cu(CN)2 ]− or in the presence of an excess of
copper metal. Also, insoluble Cu+ compounds
such as cuprous oxide do not disproportionate
in water.
By virtue of its large ionic radius and low
electrical charge, the Cu+ ion is a soft acid.
Therefore, the chemistry of copper in the oxida-
tion state + 1 is predominated by reactions with
soft bases like iodine (CuI), sulfur (CuSCN),
or unsaturated nitrogen ligands. In contrast,
the chemistry of Cu2+ , which is smaller and
more highly charged, is dominated by hard lig-
ands like oxygen ([Cu(H2 O)6 ]2+ ) or nitrogen
([Cu(NH3 )4 ]2+ ).
Copper is very stable in fresh water and
also in sea water or alkali metal hydroxide so-
lutions. Wastewater containing organic sulfur
compounds can be corrosive to copper.
Figure 1. Pourbaix diagram for copper in highly dilute aque-
ous solution at normal temperature [35]
Corrosion [33], [34]. M. J. N. Pourbaix
has developed potential – pH equilibrium dia-
grams for metals in dilute aqueous solutions
[35]. Such graphs give a rough indication of the
feasibility of electrochemical reactions. Figure 1
shows the behavior of copper at room temper-
ature and atmospheric pressure. The Cu – H2 O
system contains three fields of different charac-
ter:

1) Corrosion, in which the metal is attacked
2) Immunity, in which reaction is thermody-
namically impossible
3) Passivity, in which there is no reaction be-
cause of kinetic phenomena
Gases and Copper [36], [37]. An exact
knowledge of the behavior of solid and liquid
copper toward gases is important for production
and use of the metal. With the exception of hy-
drogen, [1333-74-0], the solubility of gases in
molten copper follows Henry’s law: the solubil-
ity is proportional to the partial pressure.
Oxygen [7782-44-7] dissolves in molten cop-
per as copper(I) oxide up to a concentration of
12.6 wt % Cu2 O (corresponding to 1.4 wt % O)
(also see Fig. 32). Copper(I) oxide in solid cop-
per forms a separate solid phase.
Sulfur dioxide [7446-09-5] dissolves in
molten copper and reacts:
6 Cu + SO2
Cu2 S + 2 Cu2 O
Hydrogen is considerably soluble in liquid cop-
per, and after solidification some remains dis-
solved in the solid metal, although copper does
not form a hydride. The solubility follows Siev-
ert’s law, being proportional to the square root
of the partial pressure because the H2 molecules
dissociate into H atoms on dissolution. Hydro-
gen has high diffusibility because of its ex-
tremely small atomic volume.
Hydrogen dissolved in oxygen-bearing cop-
per reacts with copper(I) oxide at high tempera-
tures to form steam:
−→
Cu2 O + 2 H ←− 2 Cu + H2 O(g)
Steam is not soluble in copper; therefore, it ei-
ther escapes or forms micropores.
Nitrogen, carbon monoxide, and carbon diox-
ide are practically insoluble in liquid or solid
copper. Hydrocarbons generally do not react
with copper. An exception is acetylene, which
reacts at room temperature to form the highly
explosive copper acetylides Cu2 C2 and CuC2 ;
therefore, acetylene gas cylinders must not be
equipped with copper fittings.
4. Occurrence
In the upper part of the earth’s crust (16 km
deep), the average copper content is ca. 50 ppm.
Copper 7
It is thus about half as abundant as chromium,
about twice as abundant as cobalt, and 26th in
order of abundance of the elements in the acces-
sible sphere of the earth. Table 5 shows average
copper contents in natural materials.
Table 5. Typical copper contents of natural materials
Mineral Content, ppm
Basalt 85
Diorite 30
Granite 10
Sandstone 1
Copper ores (poor) 5 000
Copper ores (rich) 50 000
Native copper 950 000
Seawater 0.003
Deep-sea clays 200
Manganese nodules 10 000
Marine ore sludges 10 000
Earth’s crust (average) 50
Meteorites (average) 180
4.1. Copper Minerals
More than 200 minerals contain copper in defin-
able amounts, but only about 20 are of impor-
tance as copper ores (Table 6) or as semiprecious
stones (turquoise and malachite). Copper is a
typical chalcophilic element; therefore, its prin-
cipal minerals are sulfides, mostly chalcopyrite,
bornite, and chalcocite, often accompanied by
pyrite, galena, or sphalerite.
Secondary minerals are formed in sulfide ore
bodies near the earth’s surface in two stages.
In the oxidation zone, oxygen-containing wa-
ter forms copper oxides, basic salts (basic car-
bonates and basic sulfates), and silicates. In the
deeper cementation zone, copper-bearing solu-
tions from these salts are transformed into sec-
ondary copper sulfides (chalcocite and covel-
lite) and even native copper of often high purity,
e.g., in the Michigan copper district (Keweenaw
Peninsula).
Other metallic elements frequently found in
copper ores are iron, lead, zinc, antimony, and ar-
senic; less common are selenium, tellurium, bis-
muth, silver, and gold. Substantial enrichments
sometimes occur in complex ores. For example,
ores from Sudbury, Ontario, in Canada contain
nickel and copper in nearly the same concentra-
tions, as well as considerable amounts of plat-
inum metals. The copper ores from Zaire and
8 Copper
Table 6. The most important copper minerals

Mineral Formula Copper, wt % Crystal system Density, g/cm3

Native copper Cu
99.92 cubic 8.9

Chalcocite Cu2 S 79.9 orthorhombic 5.5 – 5.8
Digenite Cu9 S5 78.0 cubic 5.6
Covellite CuS 66.5 hexagonal 4.7
Chalcopyrite CuFeS2 34.6 tetragonal 4.1 – 4.3
Bornite Cu5 FeS4 /Cu3 FeS3 55.5 – 69.7 tetragonal 4.9 – 5.3
Tennantite Cu12 As4 S13 42 – 52 cubic 4.4 – 4.8
Tetraedrite Cu12 Sb4 S13 30 – 45 cubic 4.6 – 5.1
Enargite Cu3 AsS4 48.4 orthorhombic 4.4 – 4.5
Bournonite CuPbSbS3 13.0 orthorhombic 5.7 – 5.9
Cuprite Cu2 O 88.8 cubic 6.15
Tenorite CuO 79.9 monoclinic 6.4
Malachite CuCO3 · Cu(OH)2 57.5 monoclinic 4.0
Azurite 2 CuCO3 · Cu(OH)2 55.3 monoclinic 3.8
Chrysocolla CuSiO3 · n H2 O 30 – 36 (amorphous) 1.9 – 2.3
Dioptase Cu6 [Si6 O18 ] · 6 H2 O 40.3 rhombohedral 3.3
Brochantite CuSO4 · 3 Cu(OH)2 56.2 monoclinic 4.0
Antlerite CuSO4 · 2 Cu(OH)2 53.8 orthorhombic 3.9
Chalcanthite CuSO4 · 5 H2 O 25.5 triclinic 2.2 – 2.3
Atacamite CuCl2 · 3 Cu(OH)2 59.5 orthorhombic 3.75

Zambia are useful sources of cobalt. Many por-
phyry copper ores in America contain significant
amounts of molybdenum and are the most im-
portant single source of rhenium. The extraction
of precious metals and other rare elements can
be decisive for the profitability of copper mines,
smelters, and refineries.
4.2. Origin of Copper Ores
Ore deposits are classified according to their
mode of formation, but the origin of copper ores
is geologically difficult to unravel, and some
of the proposed origins are controversial. The
classification distinguishes two main groups, the
magmatic series and the sedimentary series.
Magmatic ore formation involves magma
crystallization and comprises the following
groups:
1) Liquid magmatic ore deposits originate by
segregation of the molten mass so that the
heavier sulfides (corresponding to matte)
separate from the silicates (corresponding
to slag) and form intrusive ore bodies. Ex-
amples: Sudbury, Ontario; Norilsk, western
Siberia.
2) Pegmatitic – pneumatolytic ore deposits de-
velop during the cooling of magma to ca.
374 ◦ C, the critical temperature of water. Ex-
amples: Bisbee, Arizona; Cananea, Mexico.
3) Hydrothermal ore deposits result by further
cooling of the hot, dilute metal-bearing solu-
tions from ca. 350 ◦ C downward, i.e., below
the critical temperature of water. Such de-
posits contain copper primarily as chalcopy-
rite and satisfy ca. 50 % of the demand in
the Western world. There are many exam-
ples of different types of hydrothermal de-
posits. Examples: Butte, Montana (gangue
deposit); Tsumeb, Namibia (metasomatic
deposit); Bingham Canyon, Utah; Chuquica-
mata, Chile; Toquepala, Peru; Bougainville,
Solomon Islands (impregnation deposits).
Impregnation deposits are also called dis-
seminated copper ores or porphyry copper
ores (or simply porphyries) because of their
fine particle size.
4) Exhalative sedimentary ore deposits origi-
nate from submarine volcanic exhalations
and thermal springs that enter into seawa-
ter, and constitute a transitional type to sedi-
mentary deposits. These ores are third in eco-
nomic importance in the Western world. The
actual formation of such sulfidic precipita-
tions can be observed, for example, the ma-
rine ore slimes in the Red Sea. Examples:
Mount Isa, Queensland; Rio Tinto, Spain;
Rammelsberg (Harz), Federal Republic of
Germany.
The origin of sedimentary ore occurs in the
exogenous cycle of rocks and may be subdivided
into the following groups:
 Copper 9

1) Arid sediments in sandstones and conglom- 4.4. Copper Resources

erates occur widely in the former Soviet
Union as widespread continental zones of
weathering with uneven mineralization. Ex-
amples: Dsheskasgan, Kazakhstan; Exótica,
Chile.
2) Partly metamorphized sedimentary ores in
shales, marls, and dolomites form large
strata-bound ore deposits, especially in the
African copper belt, and represent the second
most important source of copper to the West-
ern world, as well as supplying nearly 75 % of
its cobalt. Examples: Zaire (oxidation zone,
oxidized ores
6 % Cu); Zambia (cementa-
tion zone, secondary sulfide ores
4 % Cu).
3) Marine precipitates have formed sedimen-
tary ore deposits similar to the present phe-
nomenon of sulfide precipitation by sulfur
bacteria in the depths of the Black Sea. Ex-
amples: Silesia (copper marl), Poland.
4) Deep-sea concretions lie in abundance on the
bottom of the oceans, especially the Pacific
Ocean. These so-called manganese nodules
World primary copper reserves were estimated
in 1991 at 552 × 106 t (Table 7) [41]. Reserves
are identified resources and do not include
undiscovered resources. With time the avail-
able reserves have increased because of techni-
cal progress in processing ores with low copper
content and the discovery of new ore deposits
[38], [39]. About 321 × 106 t were classified as
minable copper ores under the technical and eco-
nomical conditions at that time.
It is believed that a large potential of as-yet
untouched deposits exist. Therefore, the poten-
tially usable copper resources are estimated to
be about three times as large as the reserve base.
In addition to ores on land, there is an estimated
amount of copper in deep-sea nodules of about
0.7 × 109 t.
Table 7. Copper ore reserves in 1991 [41]
Country Ore reserves, Percentage of
106 t world reserves

could also be a source of copper in the future. United States 90 16.3

Chile 120 21.7
Peru 31 5.6
Zambia 30 5.4
Zaire 30 6.3
4.3. Copper Ore Deposits Canada 23 4.2
Australia 21 3.8
Geologically, the main regions of copper ore de- Philippines 16 2.9
posits are found in two formations: the Precam- Indonesia 8 1.4
China 8 1.4
brian shields and the Tertiary fold mountains and Poland 15 2.7
archipelagos. There are major producing coun- CIS 54 9.8
Other countries 106 19.2
tries on every continent [38], [39].
North America: United States (Arizona, Utah, If one assumes that total production of pri-
New Mexico, Montana, Nevada, and Michi- mary copper will remain stable, the identified
gan), Canada (Ontario, Quebec, British reserves would last until 2040. With an increase
Columbia, and Manitoba), and Mexico in copper production of 2 – 3 %, which is more
(Sonora) realistic, the duration of the known reserves will
South America: Chile, Peru, Argentina, and be reduced. However, these forecasts are quite
Brazil unreliable because the growing use of secondary
Africa: Zaire, Zambia, Zimbabwe, South copper (recycling materials) and the discovery
Africa, and Namibia of new copper ore deposits are not considered.
Australia and Oceania: Queensland, Papua New
Guinea
Asia: Former Soviet Union (Siberia, Kaza-
khstan, and Uzbekistan), Japan, Philippines,
4.5. Mining
Indonesia, India, Iran, and Turkey
Exploration, which is the search for ore deposits
Europe: Poland (Silesia), Yugoslavia, Portugal,
and their detailed investigation, is required to
Bulgaria, Sweden, and Finland
Antarctica may be an important source of
copper ores in the foreseeable future.
10 Copper
ascertain the commercial feasibility of a poten-
tial mine. The used geological, geochemical, or
geophysical methods are complicated and ex-
pensive. But often legal and political factors are
more decisive for a new mine project than tech-
nological or financial aspects. The methods used
for exhausting the copper ore are depending to
a great extent to the type of deposit. Important
parameters are metal content of the ore and ge-
ometry and depth of the ore body. These pa-
rameters determine the working method. Under-
ground and open-cast mining are the two basic
techniques. As a generalization mining can be
divided into the stages drilling, blasting, load-
ing, and haulage of the ore.
Technological developments like the LHD
technique (load, haul, dump) and the use of
concrete for stowing have made mining more
cost efficient. But underground mining is still
more labor-intensive and expensive than open
cast mining. Therefore, copper ores with an av-
erage Cu content of 1 % or more or that con-
tain other valuable metals in addition to copper
(e.g., precious metals, nickel, cobalt) are mined
underground, while ores with 0.5 % Cu, which
represents a 100-fold enrichment of the average
copper content in the earth’s crust, are mined
by open-cast methods. The porphyry copper de-
posits which are located near the surface can
only be exploited by open-cast technique. They
have become more important during the last
decades. The first open pit was started at Bing-
ham Canyon early this century. Today the ter-
raced copper open pits are the largest ore mines
in the world. They often cover more than one
square kilometer and have working depths of
several hundred meters. 100 000 t of crude ore
are extracted per day. Today more than 50 % of
the primary copper comes from open pits. Other
less common methods for copper extraction are
in situ leaching or ocean mining.
In situ leaching is a hydrometallurgical pro-
cess in which copper is extracted by chemical
dissolution in sulfuric acid. This method is suit-
able for low-grade copper ore bodies for which
customary mining operations would be uneco-
nomical, as well as for the leaching of remenant
ores from abandoned mines. In some cases, the
ore body must be broken before leaching by
blasting with explosives to increase the surface
area for chemical reaction.
Ocean mining involves obtaining metallifer-
ous raw materials from the deep oceanic zones.
Two groups of substances are of interest: deep-
sea nodules [43] and marine ore slimes [44]. The
nodules (manganese nodules; see → Manganese
and Manganese Alloys, Chap. 9.) contain, in
addition to iron oxides, ca. 25 % Mn, 1 % Ni,
0.35 % Co and 0.5 % (max. 1.4 %) Cu. Spe-
cially equipped ships have collected and lifted
these nodules from depths of 3000 – 5000 m;
specific metallurgical and chemical methods for
processing the nodules have been developed in
pilot plants. Because of the extremely high ex-
penses, large-scale operations of this type have
not yet been undertaken. Marine ore slimes from
the Red Sea (2200-m depth) average ca. 4 % Zn,
1 % Cu, and a little silver. Although methods for
processing these slimes have been investigated,
this resource is not now economically important.
5. Production
Over the years copper production methods have
been subjected to a continual selection and im-
provement process because of the need for (1) in-
creased productivity through rationalization, (2)
lower energy consumption, (3) increased envi-
ronmental protection, (4) increased reliability of
operation, and (5) improved safety in operation.
During this development a number of tendencies
have become apparent:
1) Decrease in the number of process steps
2) Preference for continuous processes over
batch processes
3) Autogenous operation
4) Use of oxygen or oxygen-enriched air
5) Tendency toward electrometallurgical meth-
ods
6) Increased energy concentration per unit of
volume and time
7) Electronic automation, measurement, and
control
8) Recovery of sulfur for sale or disposal
9) Recovery of valuable byproducts
The selection of a particular production
method depends essentially on the type of avail-
able raw materials, which is usually ore or con-
centrate and on the conditions at the plant loca-
tion.

About 80 % of primary copper production
comes from low-grade or poor sulfide ores. Af-
ter enrichment steps, the copper concentrates
are usually treated by pyrometallurgical meth-
ods. Generally, copper extraction follows the se-
quence:
1) Beneficiation by froth flotation of ore to give
copper concentrate
2) Optional partial roasting to obtain oxidized
material or calcines
3) Two-stage pyrometallurgical extraction
a) smelting concentrates to matte
b) converting matte by oxidation to crude
(converter or blister) copper
4) Refining the crude copper, usually in two
steps
a) pyrometallurgically to fire-refined copper
b) electrolytically to high-purity electrolytic
copper
Figure 2 [13] illustrates the principal pro-
cesses for extracting copper from sulfide ore.
About 15 %, with an increasing trend, of the
primary copper originates from low-grade oxi-
dized (oxide) or mixed (oxidized and sulfidic)
ores. Such materials are generally treated by hy-
drometallurgical methods.
The very few high-grade or rich copper ores
still available can be processed by traditional
smelting in a shaft furnace. This process is also
used for recovering copper from secondary ma-
terials, such as intermediate products, scrap, and
wastes.
Figure 3 [13] illustrates the most important
operations in copper extraction from various ox-
idic ores.
5.1. Beneficiation
Sulfidic copper ores are too dilute for direct
smelting. Smelting these materials would re-
quire too much energy and very large furnace
capacities. The copper ore coming from the mine
(0.5 – 1 % Cu) must be concentrated by benefi-
ciation. The valuable minerals like chalcopyrite
are intergrown with gangue. Therefore, in the
first step the lumpy ore is crushed and milled
into fine particles (< 100 µm) to liberate the in-
dividual mineral phases.
Typical equipment for crushing to about
20 cm are gyratory and cone crushers. Then wet
Copper 11
grinding in semi-autogenous rod or autogenous
ball mills takes place. Size classification takes is
performed in cyclones. In the next step of bene-
ficiation, valuable minerals and gangue are sep-
arated by froth flotation of the ore pulp, which
exploits the different surface properties of the
sulfidic copper ore and the gangue [46]. The hy-
drophobic sulfide particles become attached to
the air bubbles, which are stirred into the pulp,
rise with them to the surface of the pulp, and are
skimmed off as a froth of fine concentrate. The
hydrophilic gangue minerals remain in the pulp.
Organic reagents with sulfur-containing groups
at their polar end, such as xanthates, are used as
collectors in the flotation process. Additionally,
modifiers like hydroxyl ions (pH adjustment)
are used to select different sulfide minerals, for
example, chalcopyrite and pyrite. Alcohols are
used to stabilize the froth.
To obtain concentrates with highest possible
purity and recovery rate, the flotation process
usually consists of several stages which are con-
trolled by expert systems. Various sensors for
particle size, pH, density, and other properties
are installed. Figure 4 gives an overview of a
typical beneficiation process at a concentrator.
In the first flotation stage, as much copper as
possible is recovered in a rougher concentrate
so that as little as possible goes to the tailings.
To increase the copper recovery rate, often these
tailings are leached with sulfuric acid. After re-
grinding, the rough concentrate is cleaned in sev-
eral flotation steps. After sedimentation in thick-
eners and filtration in automatic filter presses or
vacuum filters (ceramic disk) the typical cop-
per concentrate contains 25 – 35 % Cu and about
8 % moisture. The moisture content of the con-
centrate is a compromise between transporting
water (cost) and avoiding dust generation dur-
ing transport. Dewatered concentrates may heat
spontaneously or even catch fire; therefore, ap-
propriate precautions must be taken [47].
Copper concentrators typically treat up to
100 000 t of ore per day. They are located directly
at the mines to achieve low transport costs. The
copper recovery efficiency is over 90 %. About
95 % of the ore input goes into the tailings, which
are stored in large dams near the mine and are
used for water recycling to the flotation stages.
Separation of special copper ores such as
those containing molybdenite or with high zinc
12 Copper

Figure 2. Principal processes for extracting copper from sulfide ore

 Copper 13

Figure 3. Principal processes for extracting copper from oxidic ore [45]
14 Copper
Figure 4. Overview of a typical beneficiation process at a concentrator
or lead content (Canada) is also possible by flota-
tion methods. Flotation of non-sulfide copper
minerals is rare because these ores are mostly
subjected to hydrometallurgical copper recov-
ery, for example, heap leaching. In Zambia and
Zaire, however, siliceous copper oxide ores are
floated with fatty acid collectors, and dolomitic
copper oxide ores are sulfidized with sodium hy-
drogensulfide and then floated [48].
5.2. Roasting
Roasting can be used to prepare sulfide concen-
trates for subsequent pyrometallurgical or hy-
drometallurgical process. Partial roasting under
oxidizing conditions may be carried out prior
to smelting in reverberatory or electric furnaces.
Complete oxidizing or sulfatizing roasting may
be performed before leaching operations, espe-
cially if other valuable metals such as cobalt are
present in the concentrate. Reducing roasting
may be carried out if copper concentrates with
very high contents of impurities such as As are
to be smelted.
However, roasting processes are today not
very important for the copper extraction pro-
cess. Only a few plants are still operating, for
example Boliden’s Rönnskär Smelter [211] and
Bor Smelter [212]. Since ca. 1975 combined
roasting and matte smelting processes such as
flash smelting have been favored because of their
lower energy consumption and process gas han-
dling advantages.
The roasting process has several effects:
1) Drying the concentrates
2) Oxidizing a part of the iron present
3) Controlling the sulfur content
4) Partially removing volatile impurities, espe-
cially arsenic
5) Preheating the calcined feed with added
fluxes, chiefly silica and limestone
Chemical Reactions. When the moist con-
centrates, which contain many impurity ele-
ments, are heated, a multitude of chemical reac-
tions occur. Because analysis of the many ther-
modynamic equilibria is not practical, a few fun-
damental systems are usually chosen. The most
important is the ternary copper – oxygen – sulfur
system (Fig. 5). The next most important system
is the ternary iron – oxygen – sulfur system be-
cause most sulfidic copper ores contain signifi-
cant amounts of iron.
Initially, sulfides such as pyrite and chalcopy-
rite decompose and generate sulfur vapor, which
reacts with oxygen to form sulfur dioxide:
FeS2 −→ FeS + S(g)
 Copper 15

2 CuFeS2 −→ Cu2 S + 2 FeS + S(g) Methods. There are several important roast-
ing methods; all involve oxidation at an elevated
S(g) + O2 (g) −→ SO2 (g)
temperature, generally between 500 and 750 ◦ C:

The principal reactions, i.e., the formation of
metal oxides, sulfur trioxide, and metal sulfates,
are exothermic.
MS + 1.5 O2
MO + SO2
SO2 + 0.5 O2
SO3
MO + SO3
MSO4
In addition, there are secondary reactions, such
as the formation of basic sulfates, ferrites (espe-
cially magnetite), and silicates, the last provid-
ing most of the slag in the subsequent smelting:
MO + MSO4 −→ MO · MSO4
MO + Fe2 O3 −→ MFe2 O4
1) Partial (oxidizing) roasting is the conven-
tional way of extracting copper from sul-
fide concentrates. At 700 – 750 ◦ C, the de-
gree of roasting is determined by controlling
the access of air. A predetermined amount of
sulfur (30 – 50 % is removed, and only part
of the iron sulfide is oxidized. The copper
sulfide is relatively unchanged. These con-
ditions are important for the formation of a
suitable matte.
2) Total, or dead, roasting is occasionally used
for complete oxidation of all sulfides for a
subsequent reduction process or for special
hydrometallurgical operations.
3) Sulfatizing roasting is carried out at
550 – 650 ◦ C to form sulfates. This method
yields calcines well-suited for hydrometal-
lurgical treatment.

FeO + Fe2 O3 −→ Fe3 O4 Roasters. Industrial roasting is done in two

types of roasters: fluidized-bed and multiple-
MO + SiO2 −→ MSiO3 hearth roasters. Both are continuously operated
processes.
Oxidizing roasting is usually carried out in
fluidized-bed roasters with short residence times
Representative reductive roasting reactions are: in the range of seconds and high production rates
up to 50 t of moist concentrate per hour. The
FeS2 −→ FeS + S(g)
oxidation reactions supply most of the required
heat. About 30 – 50 % of the incoming sulfide
8 FeAsS −→ 4 FeAs + 4 FeS + As4 S4 (g)
is oxidized to SO2 by using slightly oxygen en-
riched air (up to 30 % O2 ). The off-gas is rich
in SO2 (6 – 12 %) and suitable for conversion to
sulfuric acid. The hot calcine is usually sent to
reverberatory or electric furnace. The advantage
of a roaster in front of a smelting furnace is
the lower energy requirement of the smelting
furnace and the higher matte grade. Examples
of fluidized-bed roasters are Boliden Rönnskär
(Sweden), Bor Smelter (Yugoslavia) in front of
pyrometallurgical copper extraction, and Cham-
bishi (Zambia) ahead of a leaching plant.
Reductive roasting is usually carried out in
multiple-hearth furnaces because of the long res-
idence time (several hours) and the precise con-
trol of temperature and gas composition on each
hearth. These roasters have lower production
Figure 5. Partial phase diagram of the ternary Cu – O – S
system [51] rates and are fired by natural gas burners. An ex-
ample for the reducing process is the treatment
16 Copper

of El Indio (Chile) concentrate, which contains palladium, collect almost entirely in the matte,
8 % As and about 22 % Cu. About 97 % of the ar- whereas calcium, magnesium, and aluminum go
senic is removed during the roasting process at into the slag.
about 650 – 720 ◦ C [213]. In former times the
Table 8. Average percentage distribution of the accompanying ele-
multiple-hearth roasters (Herreshoff furnaces) ments in copper smelting, p. 591[20]
were widely used for the extraction of copper
Element Matte Slag Flue
from concentrates. dust

Arsenic 35 55 10
Antimony 30 55 15
5.3. Pyrometallurgical Principles Bismuth 10 10 80
Selenium 40 – 60
Tellurium 40 – 60
Smelting of unroasted or partially roasted sul- Nickel 98 2 –
fide ore concentrates produces two immiscible Cobalt 95 5 –
Lead 30 10 60
molten phases: a heavier sulfide phase contain- Zinc 40 50 10
ing most of the copper, the matte, and an oxide Tin 10 50 40
Silver and gold 99 1 –
phase, the slag. In most copper extraction pro-
cesses, matte is an intermediate.

5.3.1. Behavior of the Components 5.3.2. Matte

The most important equilibrium in copper matte
smelting is that between the oxides and sulfides
of copper and iron:
Cu2 O + FeS
Cu2 S + FeO
Iron(II) oxide [1345-25-1] reacts with added sil-
ica flux to form fayalite [13918-37-1], a ferrous
silicate that is the main component of slag:
2 FeO + SiO2 −→ Fe2 SiO4
Liquid iron sulfide [1317-37-9] reduces higher
iron oxides to iron(II) oxide:
3 Fe2 O3 + FeS −→ 7 FeO + SO2 (g)
3 Fe3 O4 + FeS −→ 10 FeO + SO2 (g)
The second reaction serves to remove magnetite
[1309-38-2], which complicates furnace opera-
tions because of its high melting point (1590 ◦ C)
[54].
The pyrometallurgical production of copper
from sulfide ore concentrates may be considered
as a rough separation of the three main elements
as crude copper, iron(II) silicate slag, and sulfur
dioxide. About 20 accompanying elements must
be removed from the copper by subsequent refin-
ing. Table 8 shows the distribution of important
impurities among matte, slag, and flue dust. Pre-
cious metals, such as silver, gold, platinum, and
The ternary Cu – Fe – S system is discussed in
detail in the literature [55–57]. Figure 6 shows
the composition of the pyrometallurgically im-
portant copper mattes and the liquid-phase im-
miscibility gap between matte and the metallic
phase. In the liquid state, copper matte is essen-
tially a homogeneous mixture of copper(I) and
iron(II) sulfides: the pseudobinary Cu2 S – FeS
system.
Arsenides and antimonides are soluble in
molten matte, but their solubility decreases with
an increasing percentage of copper in the matte.
Accordingly, when the arsenic concentration is
high, a special phase, the so-called speiss, can
separate. It is produced under reducing condi-
tions in the blast or electric furnace, and its
decomposition is complicated (→ Arsenic and
Arsenic Compounds, → Antimony and Anti-
mony Compounds).
Compositions of several copper mat-
tes are shown in the partial diagram
Cu2 S – FeS – (Fe3 O4 + FeO) (Fig. 7), which is a
section of the quaternary Cu – Fe – O – S system.
The density of solid copper mattes ranges bet-
ween 4.8 g/cm3 (FeS) and 5.8 g/cm3 (Cu2 S);
liquid mattes have the following densities:
4.1 g/cm3 (30 wt % Cu, 40 wt % Fe, 30 wt % S),
4.6 g/cm3 (50 wt % Cu, 24 wt % Fe, 26 wt % S),
and 5.2 g/cm3 (80 wt % Cu, 20 wt % S).
 Copper 17

Figure 6. Ternary Cu – Fe – S diagram showing copper mat- Figure 7. Partial ternary Cu2 S – FeS1.08 – (Fe3 O4 + FeO)
tes and the miscibility gap [55] diagram [58] showing mattes from various processes
◦ Reverberatory furnace;  Flash smelting furnace;  Elec-
tric furnace; • Blast furnace;  Converter

Table 9. Composition (wt %) of typical copper smelter slags [64]

Component Reverberatory Flash Noranda Peirce – Smith

furnace furnace reactor converter

Copper 0.4 – 0.6 1–2 8 – 10 2–8

Iron (total) 35 40 35 50
Silica 38 30 21 25
Magnetite 7 – 12 13 25 – 29 20 – 25
Ratio of Fe to SiO2 0.92 1.33 1.67 2.0

5.3.3. Slags

Slags from copper matte smelting contain

30 – 40 % iron in the form of oxides and about
the same percentage of silica (SiO2 ), mostly
as iron(II) silicate. Such slags can be consid-
ered as complex oxides in the CaO – FeO – SiO2
system [59] or, because of the relatively low
CaO content of most slags, in the partial dia-
gram FeO – Fe2 O3 – SiO2 [60] (Fig. 8). Ternary
systems of these and other pertinent oxide sys-
tems are found in the literature [61], [62]. Ta-
ble 9 shows the general composition of some
slag types. Important properties of copper slag
systems are compiled in [63].

Figure 8. Ternary FeO – Fe2 O3 – SiO2 diagram [60]

The objectives of matte smelting are to

achieve a rapid, complete separation of matte
18 Copper

and slag, the two immiscible phases, and a min- on the total oxidation of sulfide ores with subse-
imal copper content in the slag. The differing quent reduction to metal, avoiding the formation
properties of slag and matte affect this separa- of copper matte, are used only rarely because of
tion: high fuel consumption, formation of copper-rich
slags, and production of crude copper with a high
1) the low, narrow melting interval of slag level of impurities.
2) the low density of liquid slag (ca. Prior to the 1960s, the most important way of
3.1 – 3.6 g/cm3 ) and the difference in den- producing copper was roasting sulfide concen-
sity between molten matte and slag of ca. trates, smelting the calcines in reverberatory fur-
1 g/cm3 naces, and converting the matte in Peirce – Smith
3) the low viscosity and high surface tension of converters. Since that time, the modern flash
the slag smelting process with subsequent converting has
The ratio of the weight percent of copper in become predominant. Figure 9 shows the flow
matte to that of copper in slag should be bet- sheet of a modern copper smelter, from concen-
ween 50 and 100. High matte grades generally trate to pure cathode copper, including the use
cause high copper losses in slag. Such losses of oxygen, recovery of waste heat, and environ-
depend on the mass ratio of slag to copper pro- mental protection. Table 10 compares the impor-
duced, which is usually between 2 and 3. Copper tant stages and processes of copper production,
in slags occurs in various forms, including sus- showing the range of the matte composition for
pended matte, dissolved copper(I) sulfide, and each process.
slagged copper(I) oxide, partially as a silicate,
which is typical of nonequilibrium processing.
Slags containing < 0.8 % copper are sold
as products with properties similar to those of
natural basalt (crystalline) or obsidian (amor-
phous) or discarded as waste. When liquid slag
is cooled slowly, it forms a dense, hard, crys-
talline product that can be used as a large-size
fill for riverbank protection or dike construction
and as a medium-size crushed fill for roadbeds or
railway ballast. Quick solidification, by pouring
molten slag into water, gives amorphous granu-
lated slag, an excellent abrasive that has partially
supplanted quartz sand. Ground granulated slag
is used as a trace element fertilizer because of
its copper and other nonferrous metals.
Most of the newer copper smelting pro-
cesses produce high-grade mattes, and the short
residence time of the materials in the reac-
tion chamber results in an incomplete approach
to chemical equilibrium. Both factors lead to
high amounts of copper in the slag, generally
>1 wt %. Such slags must be treated by special Figure 9. Typical flow sheet for pyrometallurgical copper
production from ore concentrates [65]
methods for copper recovery (Section 5.5.1).

5.3.4. Oxidizing Smelting Processes 5.3.5. Proposals

Nearly all pyrometallurgical copper processes Numerous laboratory experiments and pilot-
are based on the principle of partial oxidation plant runs have been carried out to develop
of the sulfide ore concentrates. Methods based smelting methods based on elements other than
Table 10. Survey of pyrometallurgical processes for copper production [66]

Copper
19
20 Copper
oxygen. Two lines of development have dom-
inated, reduction with hydrogen and chlorina-
tion, but without leading to commercialization.
Reduction. A potential process involves the
reduction of chalcopyrite [70]:
2 CuFeS2 + 3 H2 + 3 CaO −→ Cu2 S + 2 Fe + 3 CaS + 3 H2 O
CuFeS2 + 2 H2 + 2 CaO −→ Cu + Fe + 2 CaS + 2 H2 O
The reduction by hydrogen is endothermic,
but the overall reaction with calcium oxide is
exothermic. A similar proposal [71] is based on
the reaction of a metal sulfide with steam in the
presence of calcium oxide:
Chlorination. The reactions of chalcopyrite
with chlorine are also of interest [72]:
>500 ◦ C:
CuFeS2 + 2 Cl2 −→ CuCl2 + FeCl2 + 2 S
<500 ◦ C:
CuFeS2 + 3.5 Cl2 −→ CuCl2 + FeCl3 + S2 Cl2
followed by electrolysis of the molten copper
(I) chloride.
The recently proposed thermoelectron chlo-
rination process is another variation [73]:
CuFeS2 + 2 Cl2 −→ CuCl + FeCl3 + 2 S
Electrolysis. Another approach, to avoid
converting, proposed the electrolysis of molten
copper matte [74].
5.4. Traditional Bath Smelting
At the end of the Middle Ages, copper was pro-
duced by the German or Swedish smelting pro-
cess that involved roasting reduction with up
to seven process steps in small shaft furnaces.
Around 1700, reverberatory furnaces were con-
structed in which the ore was processed by roast-
ing, the so-called English or Welsh copper smelt-
ing process, originally with ten process steps.
The large blast and reverberatory furnaces of
the 1900s were derived from these principles.
Later, the electric furnace for matte smelting
was developed. Newer processes are the Isas-
melt/Ausmelt/Csiromelt (furnace with vertical
blowing lance), the Noranda and CMT/Teniente
reactors (developed from converters), the Rus-
sian Vanyukov, and the Chinese Bayia process.
5.4.1. Blast Furnace Smelting
The blast or shaft furnace is well-suited for
smelting high-grade, lumpy copper ore. If only
fine concentrates are available, they must first
be agglomerated by briquetting, pelletizing, or
sintering. Because of this additional step and its
overall low efficiency, the blast furnace lost its
importance for primary copper production and is
currently used in only a few places, for example,
Glogow in Poland.
Smaller types of blast furnace, however, are
used to process such copper-containing materi-
als as intermediate products (e.g., cement cop-
per or copper(I) oxide precipitates), reverts (e.g.,
converter slag, refining slag, or flue dusts), and
copper-alloy scrap.
The construction of the furnace is basically
related to that of the iron blast furnace, but
there are considerable differences in design, es-
pecially in size and shape: the copper blast fur-
nace is lower and smaller, and its cross section
is rectangular. Developments adopted from the
steel industry include use of preheated air (hot
blast), oxygen-enriched air, and injection of liq-
uid fuels.
The furnace is charged with alternate addi-
tions of mixture (copper-containing materials
and accessory fluxes such as silica, limestone,
and dolomite) and coke (which serves as both
fuel and reducing agent). There are three zones
in the furnace:
1) In the heating zone (the uppermost), water
evaporates and less stable substances disso-
ciate.
2) In the reduction zone, heterogeneous reac-
tions between gases and the solid charge take
place.

3) In the smelting zone, liquid phases react.
The usual mode of operation is reduc-
ing smelting, which yields two main prod-
ucts. Sulfide ores are used to produce a
matte (40 – 50 wt % Cu) and a disposal slag
(ca. 0.5 wt % Cu). In contrast, oxide ores are
processed directly to impure black copper
(
95 wt % Cu) and to a copper-rich slag. The
two ore types can be smelted together to pro-
duce matte and a slag with low copper content.
Another product is top gas, which contains flue
dust. Ores that contain high concentrations of
arsenic and antimony also form speiss, which is
difficult to decompose.
In Poland (KGHM Polska Meidz S.A.
Smelters in Glogow I and Legnica) the blast-
furnace technology is well adapted to Pol-
ish copper concentrates, which contain about
20 – 30 % Cu like normal chalcopyrites but also
5 – 10 % of organic carbon and only 9 – 12 % S.
Also these concentrates have relatively high lead
(up to 2.5 %) and arsenic (up to 0.3 %) content.
The organic carbon compounds provide about
40 – 60 % of the process energy; the rest is added
by coke. The matte has about 58 – 63 % Cu and
3 – 6 % Pb. The slag contains less than 0.5 %
Cu. The off-gas from the blast furnaces (three
in each plant) is mixed with the converter gases
(Hoboken Converter). It contains 7 – 10 % SO2
and is sent to sulfuric acid production. The pro-
duction figures are 80 000 t/a converter copper
in Legnica, and 200 000 t/a in Glogow I Smelter
[214].
5.4.2. Reverberatory Furnace Smelting
The reverberatory furnace dominated copper
matte smelting for much of the 1900s, because it
was an excellent process for smelting fine con-
centrate from flotation. It is a fossil fuel fired
hearth furnace for smelting concentrate and pro-
ducing copper matte. The reverbs began to de-
cline in the 1970s with the adoption of environ-
mentally and energetically superior processes
like flash smelting. Probably the last one was
erected in 1976 in Sar Chemesh, Iran. In 1980
about 100 reverbs were in operation, but in 1994
the number had decreased to about 25. As shown
in Figure 10 it is a rectangular furnace up to
10 m wide and 35 m long with internal brick lin-
ing. Throughputs of up to 1100 t/d concentrate
Copper 21
or a mixture of concentrate and calcine could
be processed. The charge is passed into the fur-
nace near the burners through the roof or lateral
openings. As fossil fuel, pulverized coal, heavy
oil, or natural gas is used. Normally the burner
is located in the front wall of the furnace. The
atmosphere is slightly oxidizing, and the maxi-
mum flame temperature is up to 1500 ◦ C. During
the 1980s oxygen – fuel burners have been set in
the roof to fire downwards directly on the top of
the bath. This increases the smelting rate by up
to 40 % and the energy efficiency to about 50 %
[76], [215]. Another invention was the sprinkler
burner for feeding concentrate, coal, and flux
from the top of the reverb [77].
The back half of the furnace is the settling
zone. A matte grade of between 35 and 60 % Cu
is produced, depending on whether concentrate
or calcine is fed. The slag has low copper con-
tent (< 1 %). Normally, the converter slag is also
fed back to the reverb. Sometimes problems with
solid magnetite accretions in the furnace occur.
The off-gas has a temperature of about
1250 ◦ C. It is diluted by the combustion air and
contains only about 1 – 2 % SO2 . This is too
low for efficient SO2 capture such as sulfuric
acid production by the contact process. Improve-
ments have been achieved by using higher oxy-
gen enrichment of the burners, but the off-gas
is still too dilute, and therefore this furnace is
unsuitable for many regions in the world be-
cause of environmental problems. Another dis-
advantage is the very high energy consumption.
The reverb has the highest energy consumption
of all copper matte smelting processes. A good
present example for operating reverbs is the Ilo
Smelter in Peru (Table 11). There two reverbs
smelt about 2000 t/d of concentrate, producing a
matte containing 35 % copper for the subsequent
Peirce – Smith converters. In the latest smelter
enlargement one reverb was replaced by an Te-
niente converter (CMT), and a sulfuric acid plant
for partial SO2 recovery was built.
5.4.3. Electric Furnace Smelting
In regions where relatively cheap electrical
power was available, electric furnaces were
built. The Scandinavian countries were the first
to perform electric matte smelting: 1929 at Sulit-
jelma, Norway; 1938 at Imatra, Finland, and
22 Copper

Figure 10. Schematic longitudinal and cross-section views through a reverberatory furnace [45]

1949 at Rönnskär, Sweden, which is still op- phase, which is heated by the electric energy.
erating. Accordingly, in the electric furnace, cheap re-
Electric furnaces have the rectangular ground fractories are sufficient for lining the walls above
plan and the dimensions of larger reverbera- the slag zone and the roof; only a common arch
tory furnaces. Along the centerline, up to six is required.
Söderberg continuous self-baking electrodes are The temperatures of both molten phases de-
used with alternating current (Table 11). pend on the submergence of the electrodes, and
the required heat is controlled by the electrical
Table 11. Examples of traditional reverberatory and electric furnaces
power supplied. Heat transfer takes place chiefly
Boliden Rönnskär Southern Peru Ilo by convection, which causes intense circulation
Smelter Smelter in the molten bath.
Type electric furnace reverbatory The current is divided into two partial cir-
Inside dimensions 24 × 6 × 3 36 × 10 × 3.4 cuits, through slag and through matte. The dif-
l × w × h, m
Electrodes/burners 6 8
ference in conductivity is great, slag : matte ra-
Smelting capacity, t/d 950 (hot calcine) 1000 (wet tio of 1 : 102 to 1 : 103 ; therefore, the depth of
concentrate) immersion of the electrodes into the liquid slag
Matte grade, % Cu 51 35
Off-gas volume, m3 /h 25 000 100 000 must be precisely controlled. As the electrodes
(STP) immerse deeper into the slag, more current flows
SO2 content, % 4.5 1.2
Energy consumption 300 kW/t concentrate 194 kg oil/t
through the matte. If they touch the matte layer,
concentrate a short circuit occurs. These considerations lead
to an approximate relation between the electri-
The smelting process in such units is similar cal power input and the depth of the slag layer:
to the operation in reverbs, but the concentrate is 6000 kVA and 0.5 m, 30 000 kW and 1.0 m, and
usually dried and roasted before charging to in- 50 000 kW and 1.5 m.
crease the smelting capacity. The converter slag The smelting capacity of electrical furnaces
is returned to the furnace. The composition of is higher than that of reverbs.
matte and slag resembles that of the reverb prod-
ucts, but the content of magnetite is lower. No Brixlegg Process. Lurgi developed and prac-
fuel is burned, and the volume of waste gases ticed at Brixlegg, Tirol, Austria, a modification
and the quantity of flue dust are small. The SO2 of the old roasting reaction process. Nearly dead-
content of the waste gas can be 10 %. The off-gas roasted concentrates are reduced in batches by
also contains carbon oxides from the consump- coal in a small special circular electric furnace
tion of the graphite electrodes. (2500 kVA, 5-m diameter). The crude copper av-
A significant difference between the electric eraged only 95 wt % Cu, and the operation has
furnace and the reverb is the inversion of the tem- been discontinued.
perature gradient in the furnace cavity. In the re-
verb, the combustion gases have the highest tem-
perature, whereas in electric matte smelting, the
waste gases are ca. 500 ◦ C cooler than the slag
 Copper 23

5.4.4. Isasmelt Furnace switched to high-grade copper matte smelting

(as it now still operates) because of excessive
The Isasmelt furnace and the closely related impurity levels in the copper anodes and to in-
Ausmelt furnace were both developed in the crease the smelting rate.
1980s on the basis of work conducted by CSIRO,
Australia [216]. The process consists of a tall
cylindrical furnace (small diameter but large
height, internally brick lined) equipped with a
vertical blowing lance. The lance is submerged
into the bath (slag) and blows oxygen-enriched
air and/or fossil fuel (natural gas). The moist
concentrate and flux material is pelletized and
fed through the roof of the furnace onto the bath.
Most of the energy requirement comes from the
reaction of the concentrate. The lance is made
from stainless steel. It is cooled by swirling the
air in the annulus between the pipes so that a
protective layer freezes on that part of the lance
which is immersed in the slag bath (0.3 m) [217].
The lance has to be replaced from time to time,
for example, once a week. In the continuous Isas
process, an emulsion of matte and slag is pro-
duced, which is tapped periodically to a electric
or fuel-fired settling furnace for matte/slag sep-
aration. The off-gas is high in SO2 . For cooling
it passes through a waste-heat boiler.
Two Isasmelter for copper matte are running
(Mount Isa, Australia; Cypus Miami, Arizona).
Figure 11 shows the Cyprus furnace schemati-
cally. About 90 t/h of copper concentrate is pro- Figure 11. Isasmelt furnace
cessed, and about 45 t/h of matte is produced
(58 % Cu). The off-gas contains about 35 % SO2 The Noranda furnace [219] is a horizontal
directly behind the furnace and is then diluted by steel barrel with an inner brick lining (Figure 12.
air to 8 – 9 %. The Isasmelt process has replaced The diameter is about 5 m and it is about 20 m
the electric (reverberatory) furnace, which is long. The process runs continuously. At one end
now used for matte/slag settling. Smaller Isas- of the reactor, pelletized wet concentrate, coal,
melt or Ausmelt furnaces have also been pro- flux, revert materials, and scrap are thrown into
posed or built for secondary copper smelters and the furnace and on to the top of the molten bath
primary smelters like in China. It is possible to by a high-speed slinger belt. Feeding fine con-
run the process batchwise, smelting and con- centrate through the tuyeres is also possible. The
verting the material in the furnace for producing feed material is absorbed and melted in the liquid
blister copper. Also Isasmelt furnaces have been matte/slag bath. On the side there are 20 – 40 tuy-
built for lead refining. eres in the cylindrical part of the vessel. Oxygen-
enriched air (ca. 40 % O2 ) is blown through these
tuyeres into the matte phase. The tuyeres have to
5.4.5. Noranda Process be punched periodically, as in a Peirce – Smith
The Noranda process was initially constructed converter. A layer of matte and slag must always
as a continuous smelting and converting process be present in the furnace.
which produced blister copper from copper con- The oxidation reaction of the sulfides (mostly
centrate. The first reactor was built in 1973 at iron sulfide) and the added coal provide the pro-
Horne smelter [105]. This direct-to-blister pro- cess energy. Matte is tapped at the bottom of
cess operated from 1973 to 1975 [218]. It was the vessel. Slag is periodically tapped at the
24 Copper
other end of the cylindrical furnace where there
are no tuyeres and the bath is quiet enough for
matte and slag settling. The matte usually con-
tains 70 – 75 % Cu (white metal) and is sent to
a subsequent converter. This operation gives a
large heat evolution from Fe and S oxidation in
the Noranda furnace. This avoids excessive re-
tention of impurities like Sb in the matte. The
slag contains about 3 – 7 % copper and goes to
further treatment like electric furnace or solidifi-
cation/comminution/flotation. The off-gas con-
tains about 15 – 20 % SO2 . It passes through the
large mouth at the top of the reactor into a hood
and is sent to cooling, cleaning, and sulfuric acid
production. In case of emergencies the furnace
can be rolled out so that the tuyeres have a secure
position above the molten bath.
Figure 12. Noranda furnace
The Noranda process is well suited for smelt-
ing scrap and residues, ashes, precious metals
scrap, telephone scrap, and computer/electronic
scrap. Due to the high temperature and smelting
intensity, potentially harmful organics are oxi-
dized to CO2 and H2 O. The productivity can be
increased by using higher oxygen enrichment.
Then less fossil fuel is needed and the amount
of off-gas decreases.
5.4.6. CMT/Teniente Process
The Caletones Matte Treatment (CMT) or so
called Teniente process [220], [221] is similar to
the Noranda process. The important differences
are that no coal is included in the charge and
molten low-grade copper matte is periodically
added as fuel. Therefore, the Teniente furnace is
mostly regarded as a converter.
The process was developed at Teniente
Smelter by adding dry concentrate to a
Peirce – Smith converter for increasing exist-
ing smelter capacity. The Teniente process has
been widely adopted in Latin America. Like
the Noranda reactor, it is a robust technology
but has still not demonstrated that it can meet
the highest environmental standards. The fur-
naces are horizontal cylinders, 4 – 5 m in diam-
eter and 14 – 22 m long (Figure 13). Inside, the
converter is brick-lined, and it has 30 – 50 tuy-
eres for blowing oxygen-enriched air (30 – 32 %
O2 ). Solid feed such as wet concentrate, flux,
or recycled materials are blown continuously
through a high-pressure gun (Garr gun) on the
top of the molten bath. Dry concentrate is in-
jected additionally through four or five tuyeres
in the bath. Molten matte (35 – 40 % Cu) coming
from a reverb is added periodically through the
mouth of the converter. The temperature in the
converter is controlled by the ratio of wet (low-
ers temperature) and dry (increases temperature)
feed material.
High-grade matte (72 – 77 % Cu) is produced
and tapped periodically to the subsequent con-
verting step. Slag with 4 – 7 % Cu is tapped for
further processing. The off-gas is collected by a
water-cooled hood above the mouth of the con-
verter. The off-gas is mixed with air because the
hood is not tight to the converters mouth. There-
fore, the SO2 content is only about 10 %. The
gas is cooled with water sprays, the flue dust is
stripped and then the gas is sent to sulfuric acid
production (or in some cases to the stack).
With its molten-matte requirement, the CMT
is dependent on the operation of a reverbera-
tory furnace with all the associated environmen-
tal problems (SO2 emission). To overcome this
reliance, some possibilities have been tested,
all of which increase the energy in the vessel:
increased oxygen enrichment of the blast, in-
creased injection of dry concentrate through the
tuyeres, and burning small amounts of fossil
fuel. Today there are CMTs which do not need
low-grade molten matte.
5.4.7. Vanyukov Process
The Vanyukov process was developed in the
1970s in Norilsk, Russia. It is similar to the No-
randa process, but the furnace is rectangular with
tuyeres on both sides, blowing highly enriched
air ( 70 – 90 % O2 ) in the slag zone (Figure 14).

Figure 13. Teniente converter (CMT)
Moist copper concentrate is charged through
ports in the roof of the furnace. The process pro-
duces matte (ca. 50 % Cu), slag (1.5 – 2 % Cu)
and off-gas (ca. 30 % SO2 ). The furnace oper-
ates continuously, and the matte and slag leave
the furnace continuously through two siphons.
The matte is sent to converting process, and the
slag is cleaned in an electric furnace [222], [223].
In contrast to the Noranda furnace the
Vanyukov reactor is stationary. The tuyeres can
not be tilted out of the bath in emergency situ-
ations. The advantage of the stationary system
is the simple and very efficient SO2 capture. Six
Vanyukov furnaces are running in the CIS. With
a relatively small furnace (10 m long, 2 m wide,
and 6 m high) about 1500 to 2000 t/d concentrate
can be processed.
All the submerged-tuyere processes like No-
randa, CMT, and Vanyukov have relatively short
campaign lifetimes (one year) because of high
erosion in the tuyere zone.
5.4.8. Baiyin Process
At the Baiyin Copper Smelter in China, a process
similar to the Noranda furnace was developed
in the 1980s [78]. Concentrate is added on the
top of the molten bath, and air/oxygen is blown
through submerged tuyeres into the melt. The
Baiyin furnace has a wall inside to divide the re-
action and the settling zone. In China there are
at least two furnaces in operation, but few data
are available.
Copper 25
5.5. Autogenous Smelting
Autogenous smelting involves the use of com-
bustion heat generated by reactions of the feed
in an oxidizing atmosphere in which the sulfide
concentrate acts partly as a fuel. The formerly
separate steps of roasting and smelting are com-
bined into a roast – smelting process. The spatial
and temporal coupling of exothermic and en-
dothermic reactions leads to an economical pro-
cess, but the sensible heat of nitrogen in the air
causes a deficit in the heat balance. In practice,
various measures must be taken:
1) Increasing the oxygen content of the com-
bustion air and even using pure oxygen
2) Preheating combustion air with waste heat or
in a preheater
3) Combustion of natural gas, fuel oil, or pul-
verized coal in supplementary burners
To achieve autogenous operation and prevent
agglomeration of the feed, the moisture in the
concentrate must be removed by drying before
charging. The quantity of added fluxes is mini-
mized as far as practical to save energy.
Because the residence time of the sulfide par-
ticles in the reaction chamber is only a few
seconds, kinetic conditions predominate over
the thermodynamic equilibrium. The reactants
form a heterogeneous system, with the feed sus-
pended in the gas flow, thus the term smelting in
suspension.
These processes have several advantages:
1) High rate of reaction, increasing the produc-
tion rate
2) Energy savings
26 Copper
Figure 14. Vanyukov furnace
3) Low volume of off-gas and correspondingly
high concentration of SO2 and low quantity
of flue dust, if oxygen is used
However, a typical disadvantage is the high cop-
per content of the slags, and the relatively high
flue dust content in the off-gas, which can cause
problem in the waste-heat boiler.
5.5.1. Outokumpu Flash Smelting
After a preliminary test in 1946, the first full-
scale flash smelting furnace started operation in
1949 at Outokumpu Oy, Harjavalta (Finland).
Flash smelting has been the most widely adopted
copper matte smelting process since 1970. More
than 40 furnaces have been installed to replace
reverberatory furnaces or at new smelting opera-
tions. Nowadays the Outokumpu-type smelters
account for more than 50 % of world primary
smelter capacity.
Furnace Design. The flash furnace can be
envisioned as a combination of a reverb with
a roaster in which smelting takes place simul-
taneously. Figure 15 shows a Outokumpu flash
furnace designed in 1988 for smelting more than
3000 t/d of copper concentrate – a production
rate several times higher than those of earlier
furnaces. The current trend is towards even big-
ger units. The furnace is 24 m long, 7.5 m wide,
and 2 m high in the settling area. The hearth or
settler is equipped with oil or natural gas burn-
ers.
The reaction shaft is 6 m in diameter and 7 m
in height. It is equipped with one concentrate
burner. The gas off-take shaft is 9 m high and
has a diameter of 5 m. (All dimensions inside
the furnace, which is lined with chrome magne-
sia bricks.) The furnace has eight matte tapholes
and four slag tapholes. The reaction shaft and
large areas of the settler and the gas off take are
water-cooled to prevent overheating and weak-
ening of the furnace structure. The reaction shaft
of many furnaces is cooled by cascading water
outside the steel shell. The other areas are usu-
ally cooled by special copper cooling jackets,
which are built into the furnace walls [224].
Figure 15. Outokumpu flash smelting furnace
An important feature of the flash smelter is
the concentrate burner, which suspends the feed
particles in the oxygen-enriched air in the hot
reaction shaft. The aim is to ensure a rapid, uni-
form (over the shaft, to prevent hot spots), and ef-
ficient concentrate oxidation and generate min-
imum flue dust. Older flash smelters have four
burners, but nowadays a single burner is used
because it is easier to control the burner param-
eters. The burner (Fig. 16) consists of two con-
centric pipes: a central pipe for the solid feed
and an annulus for the oxygen-enriched blast. In
the inner pipe a distributor cone is installed to
optimize the particle distribution [225]. The gas
velocity out of the burner is up to 200 m/s.
 Copper 27

centrations the in the matte are also possible, for

example, before a flash converting process.
The matte is tapped as needed by the sub-
sequent converting step. Slag is tapped nearly
continuously. The slag contains 1 – 2 % of cop-
per, mainly in matte droplets. The slag tem-
perature is about 1230 – 1250 ◦ C; the matte is
about 30 – 50 ◦ C cooler. Typical operating data
are shown in Table 12.
Table 12. Operating data for Outokumpu flash furnaces

Norddeutsche BHP Magma Metals,

Affinerie, Hamburg, San Manuel, Arizona
Germany

Furnace 1972 1988

commissioning date
Size, inside brick, m 6 × 20 × 3 7.5 × 24 × 2
hearth w × l × h
reaction shaft d × h 6×9 6 × 6.9
Concentrate 2000 (30 – 34 % Cu) 3000 (30 % Cu)
throughput, t/d
Blast temperature, 400 – 420 25
◦
C
Oxygen enrichment, 45 – 55 60 – 80
%
Figure 16. Schematic of a flash furnace concentrate burner Blast flow-rate, m3 /h 25 000 51 000
(STP)
Flash furnaces need auxiliary equipment like Matte grade, % Cu 63 63
solids dryers (rotary, flash, or steam dryers), de- Off-gas volume, 55 000 55 000
m3 /h (STP)
livery systems, oxygen plant, blower and pre- SO2 Content 25 – 30 35
heater systems, waste-heat boiler, dust recovery Recycling of in flash furnace flotation
converter slag
and recycling system, slag-treatment furnace, Slag treatment electric furnace flotation
and sulfuric acid plant for treating the highly Fossil fuel input in 0 0
SO2 enriched off-gas. shaft
Fossil fuel for settler 5 m3 /h (STP) 15 – 20 L oil/t conc.
burner natural gas/t conc.
Operation. Various sorts of concentrate and
a few flux materials (mainly silica) are blended
and then dried before feeding into the flash Slag Cleaning. In practice two methods are
smelter. Recycle materials such as flue dust from used: froth flotation and treatment in small
the waste-heat boiler and the converters or oth- electric slag furnaces. The decision for one or
ers are also fed to the flash furnace. The process the other is determined by economics. In froth
operates continuously 24 h a day, and campaigns flotation the slag concentrate is returned to the
are run for as long as possible with out interrup- feed, and the tailings are discarded. The second
tion. method involves the reduction of flash furnace
The feed mixture is suspended at the top of slags in an electric furnace, which yields a matte
the reaction shaft, and sulfur and iron are oxi- and slag that is suitable for sale.
dized partly. The reactions are strongly exother-
mic, and the particles melt to form copper matte Off-gas and Flue Dust. The waste gases are
and slag. At oxygen enrichments of between 45 separated from part of the flue dust at ca. 1300 ◦ C
and 80 % (depending on concentrate composi- in the off-take shaft and pass through a waste-
tion and preheated blast), the process runs au- heat boiler for generating steam, and subse-
tothermally. Less oxygen enrichment requires quently to an electrostatic (Cottrell) precipitator
fossil fuel combustion in the reaction shaft. for separating the mass of flue dust, which is re-
The temperature in the reaction shaft is about cycled to the feed. The precleaned off-gas with
1250 – 1300 ◦ C. The optimal matte concentra- SO2 content of >20 % is usually processed to
tion is between 60 and 65 % Cu. Higher Cu con- sulfuric acid.
28 Copper

The flue dust consists chiefly of sulfates and
basic sulfates of copper, lead, and zinc, as well
as some volatile compounds of arsenic, anti-
mony, bismuth, and selenium. Repeated recy-
cling makes it possible to enrich selected ele-
ments for later extraction. The quantity of flue
dust is between 4 and 10 % of the input.
blast air, the process has approached the princi-
ple of INCO flash smelting. On the other hand,
newer developments aim at the production of
blister copper or white metal (75 – 80 wt % Cu)
from concentrates in only one vessel, thereby
approaching continuous smelting and convert-
ing as in the Noranda process.

Process Control. Five main parameters have

to be controlled and adjusted carefully to obtain
the highest smelting rate of concentrate, constant
matte composition, specified slag composition
and furnace temperatures, and minimum energy
consumption:
1) Concentrate feed rate
2) Flux and recycled materials feed rate
3) Blast input and temperature
4) Oxygen enrichment of the blast
5) Fossil fuel combustion
In the flash smelters constructed between
1980 and 1999 most of these parameters are
measured and adjusted automatically.
5.5.2. Inco Flash Smelting
Inco Metal Co. was the first company in the
nonferrous metal industry to use commercially
pure oxygen for autogenous flash smelting. Af-
ter tests in the late 1940s, two smaller furnaces
went into operation in 1953 [82]. Today a total
of five Inco furnaces are operating worldwide
(including Ni/Cu and one older plant in Uzbek-
istan [83]). Since 1990 no Inco furnace has been
built.

Special Operations. There are several vari-

ations on the Outokumpu flash smelting process.
Two Outokumpu copper smelters (Tamano,
Japan and Pasar, Philippines) have inserted car-
bon electrodes in the settler. The electrodes are
submerged in the slag layer to heat the slag with
electric power. The system was installed to re-
cover Cu from the slag and reduce magnetite Figure 17. Inco flash smelting furnace
without using an additional slag-cleaning fur-
nace [80], [226]. The system at Tamano Smelter
Furnace Design. In contrast to Outokumpu-
ceased operation in 1988 because the opera-
type furnaces the Inco process uses pure com-
tors found that combustion of coke – oil mixtures
mercial oxygen (95 – 98 %) instead of enriched
also gives low copper content in the slag (0.6 %)
air. The oxygen blast and concentrate are fed
[227].
through the burners (generally two) in the side
Occasionally molten converter slag is recy-
walls of the furnace. The furnace is smaller than
cled through the flash furnace like in a reverb. It
the Outokumpu furnace and has only one shaft,
is added from ladles through a spoon and launder
which is located at the center of the roof and
system high on the flash furnace [228].
takes the off-gas to the cooling system. Using
At two smelters in the world Outokumpu
pure oxygen makes the off-gas volume much
flash furnaces are used to smelt blister directly
smaller than in the Outokumpu furnace. Fig-
from concentrate (see Section 5.8).
ure 17 shows a sectional view of an Inco flash
furnace. The burner is completely different from
Trends. The diversity of modified furnace the Outokumpu type. It has low velocity of about
constructions and operating methods shows the 30 m/s into the furnace. This gives a short flame
adaptability of the Outokumpu process to dif- and also low flue dust generation. The Inco fur-
ferent raw materials and smelter locations. As nace is not equipped with other fossil-fuel burn-
increasing oxygen content has been used in the ers. Because of the small size of the furnace and

the surrounding equipment, this process is suit-
able for replacing old furnaces within existing
smelters.
Operation. Dry concentrate and flux are fed
continuously to the Inco furnace. The products
of the process are matte (50 – 60 % Cu), slag, and
off-gas with 70 – 80 % SO2 . The slag is tapped at
the sidewalls of the furnace, and the matte in the
middle part under the offtake. The temperatures
are similar to those of the Outokumpu furnace.
In contrast to an Outokumpu furnace the amount
of energy which is removed with the off-gas is
much lower because of the small off-gas quan-
tity. Therefore the Inco furnace is not equipped
with a waste-heat boiler for energy recovery. The
off-gas is cooled by different techniques such
as splash towers, cyclones, or scrubbers [229].
The absence of a waste-heat boiler avoids out-
of-service times of the furnace. Furthermore, the
copper content in the slag of the Inco furnace is
lower (0.5 – 1.5 %), and a slag-cleaning furnace
is not needed. Only Hayden Smelter operates an
additional electric furnace. Some operating data
of the Chino, New Mexico furnace are listed in
the following:
Furnace commissioning date 1984
Size, inside brick, m hearth w × l × h 5.6 × 23 × 5
gas-off take w × h 3.9 × 7.7
Concentrate throughput, t/d 1520
◦
Blast temperature, C 40
Oxygen enrichment, % 98
3
Blast flow-rate, m /h (STP) 12 500
Matte grade, % Cu 58
3
Off-gas volume, m /h (STP) 20 000
SO2 Content 75
Recycling of converter slag in flash furnace
Slag treatment discarded
Fossil fuel input 0 Concentrate ∗
Process Control. The aim of running the
Inco furnace is the same than the Outokumpu
furnace: highest throughput rates with constant
furnace properties such as matte concentration
and furnace temperatures. In comparison with
the Outokumpu process, it is more complicated
to keep the matte grade constant because the
oxygen enrichment is not adjustable. This could
be done by adjusting the mix of the feed (high
or low in copper) or adding fossil fuel for oxy-
gen consumption. But this is in conflict with the
principle of the process and does not seem eco-
nomic.
Copper 29
5.5.3. KIVCET Cyclone Smelting
Developments in power-plant technology have
led to adoption of the cyclone principle by the
metallurgical industry. The acronym KIVCET
uses the initial letters of the following Russian
terms: oxygen, vortex, cyclone, electrothermic.
The development began in 1963, and the first
plant was operated by Irtysh Polymetal Com-
bine in Glubokoe, Kazakhstan. The process is
not widely used for copper smelting.
The method is aimed at processing copper
sulfide concentrates that contain considerable
amounts of other metals. The essential part of
the continuously operated plant is the smelt-
ing cyclone, in which the concentrates are fed
vertically, and technical-grade oxygen (
95 %)
is blown in horizontally, so that reaction takes
place rapidly above 1500 ◦ C.
The furnace is divided to allow separating and
settling of the reaction products, in this respect
similar to a reverb. In contrast to the separa-
tion chamber, the atmosphere in the electrically
heated settler is maintained in a reducing state so
that the slag does not need special posttreatment.
The off-gas volume is small, and the content
of SO2 can be up to ca. 80 %. Metals are reco-
vered from the flue dust of both the separating
chamber and the settler. Table 13 and Figure 18
explain the process.
Table 13. KIVCET process: analysis and yield [84]
Analysis and yield Metal
Cu, wt % Zn, wt % Pb, wt %
Analysis
25.6 10.0 1.7
Copper matte 50.0 2.5 2.0
Slag 0.35 3.5 0.2
Yield
In matte 99.1 12.7 60.0
In oxidic condensate – 71.0 34.1
∗ Also 24.0 % Fe and 33.0 % S.
5.5.4. Contop Matte Smelting
Using a KIVCET license, KHD Humboldt
Wedag AG, Cologne developed the combined
Contop process [85]. Contop stands for continu-
ous smelting and top blowing. It is a combination
30 Copper

Figure 18. KIVCET furnace [84]

a) Smelting cyclone; b) Separating chamber; c) Cyclone waste-gas offtake; d) Partition wall; e) Settling reduction hearth;
f) Slag tap hole; g) Feed of reductant and offtake for waste gas from the hearth; h) Electrical resistance heating; i) Matte
taphole

of a high-intensity smelting process in a cyclone potential steam generation from the cyclones.
and secondary treatment of the molten phase Compared with Outokumpu flash smelting, the
with a top-blown jet. Contop-type cyclone burn- Contop process is more energy intensive (higher
ers have been used on reverberatory furnaces, specific cost per tonne of concentrate). Another
for example, at Chuquicamata and Palabora. In disadvantage is the relatively short lifetime of
1993 a complete Contop smelter started opera- the cyclone (about one year). Therefore only one
tion at El Paso (Asarco) [230], replacing the old plant was built until now.
reverberatory furnace. The furnace is shown in
Figure 19. It is a kind of a hearth furnace. Two
cyclone burners are placed on the top of one end
of the furnace. Each is fed with about 25 t/h of
dry concentrate and flux and about 95 % oxygen
blast. Natural gas is fed to the cyclone for energy
adjustment. The cyclones are made of stainless
steel and are water-cooled and about 2 m in di-
ameter and 4 m in height. Inside they are pro-
tected by a layer of solidified matte – slag. Matte
with 55 – 60 % Cu is produced. At the other
side of the furnace the off-gas is passed through Figure 19. Contop furnace
a waste-heat boiler. The amount of off-gas is
about 65 000 m3 /h (STP) with about 24 % SO2 .
Its temperature is about 1150 ◦ C. After cooling, 5.5.5. Flame Cyclone Smelting
the gas is washed and sent to sulfuric acid pro-
duction. The flame cyclone reactor (FCR) process was
To keep the slag hot, oxy-fuel burners are in- suggested by LURGI and Deutsche Babcock
stalled on the roof of the furnace between the AG ca. 1975 and has been demonstrated at a pi-
cyclones and the off-gas shaft [231]. The slag lot plant of Norddeutsche Affinerie in Hamburg
contains 0.8 % Cu and can be discarded. The ad- with a capacity of ca. 10 t/h. It is a high-tempera-
vantage of the Contop cyclone is high flexibility ture (> 1500 ◦ C) reaction for autogenous smelt-
in concentrate composition, low dust production ing of copper sulfide concentrates in a high-
(ca. 2 % of the feed material), high volatilization oxygen atmosphere (up to ca. 75 %). A sec-
of zinc and bismuth from dirty concentrates, and ond characteristic is the simultaneous removal
 Copper 31

of volatile compounds of other elements, such

as zinc, cadmium, tin, lead, arsenic, antimony,
Cu2 S + 1.5 O2 −→ Cu2 O + SO2
and bismuth, as oxides and basic salts, in the flue
dust. The SO2 content of the off-gas is greater
Cu2 O + FeS −→ Cu2 S + FeO
than 50 %. The products are a high-grade matte,
containing up to 80 % Cu, and slag, which sep- In Figure 6, the first step corresponds to moving
arates in a settler [86]. along the pseudobinary Cu2 S – FeS line to form
The principle of this method differs from that an impure copper(I) sulfide.
of the KIVCET process in that the reaction in the
FCR process takes place in a special chamber Second Step. Continuing oxidation occurs
situated before the cyclone, where the molten as in a typical roasting reaction process:
droplets are separated by centrifugal force. The
process is well suited for processing complex or
dirty concentrates, but until now never installed
in practice.

In Figure 6 and Figure 20, the composition

5.6. Discontinuous Matte Conversion moves along the Cu2 S – Cu line from the cop-
per(I) sulfide to crude metallic copper, the two
Matte produced by smelting processes is treated phases being immiscible.
in the molten state by blowing with air; this stage
of concentration is known as converting. Copper
and iron sulfides, the main constituents of matte,
are oxidized to a crude copper, ferrous silicate
slag, and sulfur dioxide.
The batch converting process has been em-
ployed for many decades in two operating steps
at ca. 1200 ◦ C in the same vessel. Investigations
and development of continuous methods are be-
ing made [87], [88].
The conventional converting of matte is
a batch process that yields in the first step
an impure copper(I) sulfide containing ca.
75 – 80 wt % Cu, the so-called white metal, and
in the second step the converter, or blister, cop-
per averaging 98 – 99 wt % Cu. The name blister
copper derives from the SO2 -containing blisters
that are enclosed in the solidified metal.

First Step. The main reactions are oxidation

of iron(II) sulfide and slagging of iron(II) oxide
by added silica [7631-86-9] flux: Figure 20. The Cu – Cu2 S system [89]

2 FeS + 3 O2 −→ 2 FeO + 2 SO2
2 FeO + SiO2 −→ Fe2 SiO4
Formation of magnetite occurs near the tuyeres:
3 FeS + 5 O2 −→ Fe3 O4 + 3 SO2
Copper(I) sulfide is partially oxidized, but it is
also reformed
The blister copper contains < 0.1 wt % S, ca.
0.5 wt % O, and traces of other impurities.
Converter Slags. The slags from the first
step are iron(II) silicates (40 – 50 wt % Fe) with
high magnetite content (15 – 30 wt % Fe3 O4 ).
The initial copper content of 3 – 8 wt % can in-
crease up to 15 wt % at the end of the reaction
by formation of copper(I) oxide. This slag can
32 Copper
be decopperized by returning it to the smelting
unit or by froth flotation (cf.page 28).
The high-viscosity small-volume converter
slags from the second step have a high copper
content (20 – 40 wt %) in the form of copper(I)
oxide or silicate. When enough slag has accumu-
lated, it is returned to the first converting stage.
Temperature. Converting is a strongly
exothermic process that can overheat during
oxidation of iron-rich mattes. The temperature
must be held ca. 1200 ◦ C by adding fluxes, cop-
per scrap, precipitates from hydrometallurgical
treatment (e.g., cement copper), or concentrates.
The off-gas (5 – 10 vol % SO2 ) is transferred to
a sulfuric acid plant.
The blowing time per batch is a few hours;
however, as the copper content of the matte in-
creases, the converting time decreases. Occa-
sionally, oxygen-enriched air is used to increase
the throughput.
Impurities. The distribution of other ele-
ments among the phases during converting is as
follows:
1) Noble metals and most of the nickel, cobalt,
selenium, and tellurium collect in white
metal and then in blister copper.
2) The bulk of zinc and some nickel and cobalt
collect in converter slag.
3) The oxides and sulfates of arsenic, antimony,
bismuth, tin, and the basic sulfates of lead are
found in flue dust.
Converter Types. The copper converter was
invented in 1880 by Manhès and David, based
on the Bessemer converter, which had been used
in the steel industry since 1855. This develop-
ment led to the incorrect name “copper besse-
merizing,” although the true Bessemer process
is a refining step. Originally, the copper con-
verter was upright, and such obsolete units were
in operation until the early 1980s, e.g., the Great
Falls converter developed by Anaconda Mining
Co., United States.
The following types are in use currently
(Fig. 21):
1) The Peirce – Smith converter has been the
most important apparatus for converting for
many decades, and the number in operation
may be in the range of a thousand. More
than 80 % of the worldwide produced cop-
per comes from this type of converter. It is
a horizontal cylinder lined with basic bricks
(magnesite, chrome – magnesite) that can be
rotated about its long axis (Fig. 22); blast air
is blown through a horizontal row of tuyeres.
In practice, the punching of tuyeres with spe-
cial devices is necessary to maintain the flow
of air. The largest vessels are 12.5 m long
with a diameter of 4.6 m.
2) Hoboken or syphon converter [91]. This vari-
ation of the P – S type was developed years
ago by Metallurgie Hoboken N.V., Belgium,
but is now used by only a few smelters in Eu-
rope and in North and South America; larger
units are operated at Glogow smelter in Sile-
sia, Poland; Cyprus Miami Smelter in Ari-
zona; and Paipote smelter (ENAMI), Chile
[92]. Its advantage is its freedom from suck-
ing in air, so the off-gas can attain SO2 levels
up to 12 %. Special features of the design are
the small converter mouth and the syphon or
goose neck that guides the off-gas and flue
dust flow.
3) Inspiration converter [93]. The vessel has two
mouths, the smaller for charging, the larger
for the off-gas. The latter is well hooded in
all operating positions. It is only in operation
at Cyprus Miami Smelter.
4) Top-blown rotary converter [95]. The TBRC,
which is known in the steel industry as the
Kaldo converter, was adopted by the nonfer-
rous industry (first by INCO, Canada) be-
cause of its great flexibility. Air, oxygen-
enriched air, or on occasion, commercial
oxygen is blown through a suspended water-
cooled lance onto the surface of a charge
of copper-containing materials. In practice,
the TBRC is used batchwise for special op-
erations on a small scale, but generally not
for converting copper matte. Tests of direct
smelting of concentrates (clean, complex,
or dirty) to white metal or blister copper
were performed at Rönnskär smelter (Boli-
den Metall AB), Sweden, but the process was
not realized technically. Copper extraction
from copper scrap and other secondary ma-
terials is also carried out. The TBRC is also
well suited for lead/precious metals metal-
lurgy.
 Copper 33

Figure 21. The evolution of the copper converter [90]

Figure 22. Schematic cross section and back view of a Peirce – Smith converter [96]
34 Copper
Developments for Increased Productivity
and Environmental Protection To increase the
productivity of a Peirce – Smith converter, usu-
ally the oxygen enrichment in the blast is in-
creased. Depending on process step (slag or cop-
per blowing) up to 30 % O2 is used. The resulting
increases in the temperature in the vessel must be
controlled. Copper smelters mostly in Europe or
Japan add copper scrap during the copper blow
phase to adjust the temperature in the converter
bath. Special systems (lift and conveyor) have
been developed to add up to 70 % of the cooling
material without stopping blowing [232], [233]
(Figure 23).
Figure 23. Machine for automatic charging of cooling ma-
terial
Automatic temperature measurement (opti-
cal spectrometer or thermocouple through the
tuyere) is used for process control and to avoid
high erosion of the brick lining of the con-
verter. Also the chemistry of the converting
process is monitored by optical spectrometry
[234]. This allows the blowing time to be easily
controlled without overblowing the charge and
thus minimizes the copper loss to the converter
slag and magnetite formation in the slag. High-
velocity tuyeres have been developed [235],
[236] which can be operated with high oxygen
enrichment without extensive refractory ero-
sion. At the front of the tuyere a tubular accre-
tion is formed which protects the brick lining.
Another advantage is that these tuyeres need not
be punched (saves labor and maintenance cost).
A disadvantage is the relatively high pressure of
about 3 bar of compressed air (high investment).
These high-velocity tuyeres have been tested in
Peirce – Smith and Hoboken converters. Today
(ca. 2000) the first smelters (Hidalgo) are plan-
ing to install the system.
One of the problems of Peirce – Smith con-
verters is leakage SO2 -containing off-gas during
charging and pouring operations in the working
environment. To avoid these fugitive emissions,
special secondary hooding systems have been
developed and installed. For example, Figure 24
shows the hooding system used at Norddeutsche
Affinerie. The collected fugitive gases are dilute
in SO2 (up to 0.2 %) and are treated by vari-
ous techniques (scrubbing with basic solutions
or dry absorption of the SO2 producing gypsum)
[237], [238].
5.7. Continuous Matte Conversion
While continuous copper matte smelting pro-
cesses have been in operation for many years,
continuous converting of matte has come into
use slowly. The potential benefits are mini-
mization of materials handling (especially over-
head crane transport of liquids), more efficient
off-gas capture, and continuous SO2 produc-
tion for the sulfuric acid plant. Two multiple-
furnace processes are used today for continuous
smelting and converting: the Mitsubishi process
and the Kennecott/Outokumpu Flash converting
process. Noranda has developed a continuously
running converter which has been in operation
since 1997 at Horne Smelter.
5.7.1. Noranda Process
In the 1970s Noranda started with the Noranda
reactor for directly smelting blister. This was
not useful and was therefore switched to smelt-
ing high-grade matte. A second reactor similar
to the smelting one is proposed for continuous
conversion of matte (patented 1985 [239]). Since
1997 it has been operated at Horne smelter. It is
a horizontal cylindrical vessel with two mouths
(one for adding liquid matte by ladle, the other
for the off-gas) and a row of submerged tuy-
eres. There is also the possibility to feed solid
matte or coal by slinger belt through one end
wall. The converter is usually fed with liquid
high-grade matte (70 % Cu) from the Noranda
smelting reactor. It produces semi-blister cop-
per with high sulfur content (1 – 1.5 %). The
semi-blister is poured into a ladle which is trans-
ported by special ladle car to the anode furnace.
The Noranda converter can be operated in four

Figure 24. Hooding system for the prevention of fugitive emissions at Norddeutsche Affinerie
modes: with molten matte feed, with any com-
bination of solid and molten matte feed, up to
100 % solid feed, in smelting mode with concen-
trate like the Noranda reactor and a conventional
Peirce – Smith converter. The converter at Horne
Smelter (Figure 25) [240] is 4.5 m in diameter
and 19.8 m long (inside the brick lining). It has
42 tuyeres. The process off-gas is collected in a
water-cooled hood and sent to the sulfuric acid
plant. The converter has a secondary ventilation
system, the gases of which are sent directly to
a stack. This process operates continuously and
has very high flexibility but not all of the poten-
tial benefits have been achieved. There is still
crane transport and handling with ladles which
causes fugitive emissions.
5.7.2. Mitsubishi Process
Mitsubishi Metals Corp., Japan, tested the
new concept during the 1960s and started the
first commercial plant at Naoshima smelter in
1974. Today (ca. 2000) four companies are op-
erating this process (Naoshima, Japan; Kidd
Creek, Canada; LG Metals, Korea; Gresik, In-
donesia). The principle of this process is the in-
terconnection of three furnaces, as shown in Fig-
ure 26 [241], [242]:
1) Smelting or S-furnace: Dried concentrates,
flux material, pulverized coal, return con-
Copper 35
verter slag, copper scrap, and flue dust are
smelted in this furnace. The fine material
(concentrate, coal) is fed through nine or
ten vertical steel lances on the top of the
molten bath. The blowing lances consist
of two concentric pipes. Through the inner
pipe, the dried concentrate is air blown, and
through the outer one, oxygen-enriched blast
(40 – 50 % O2 ). The lances are rotated to pre-
vent them sticking in the roof. They extend
to 0.5 – 1 m above the molten bath. About
0.3 – 0.5 m of the lance is consumed each day.
The off-gas contains 30 – 45 % SO2 and is
sent to sulfuric acid production.
2) Slag-cleaning furnace: Slag and matte from
the S-furnace flow continuously by grav-
ity into the elliptical slag-cleaning furnace,
which is an electric furnace with three or
six submerged graphite electrodes. The tem-
perature of the slag is kept at 1250 ◦ C.
The slag is decopperized to 0.6 – 0.9 % Cu
and discarded. The matte flows continuously
through a siphon into the converting furnace.
3) Converting or C-furnace: The matte (68 %
Cu) is converted continuously by blowing
enriched air (30 – 35 % O2 ) and CaCO3 flux
through six lances on the top of the bath. Also
copper scrap is added through the sidewall
of the furnace. Conversion only takes place
where the oxygen comes into contact with the
36 Copper

Figure 25. Noranda converter at Horne Smelter

sulfides. This is achieved by running the con- C-furnace

Diameter inside brick, m 8
verter with a special basic calcium ferrite slag Number of lances 10
(40 – 50 % Fe, 15 – 20 % CaO). The usual oxygen enrichment, % 33
silica slag is not possible because when oxy- Blast flow rate, m3 /h (STP) 25 500
Copper Scrap, t/d 190
gen is blown onto the top, solid magnetite is Off-gas volume, m3 /h (STP) 25 000
formed and blocks the surface. In the calcium SO2 in off-gas, % 26
ferrite slag dissolves the magnetite but also a
large amount of copper (15 – 18 %). The con-
The major advantage of the Mitsubishi pro-
verter slag is returned to the S-furnace. The
cess are the good SO2 capture and the lower
blister copper contains slightly more sulfur
handling expense of materials. A disadvantage
(0.7 %) than from a Peirce – Smith converter
during the initial operating time was that no
(0.02 %). It is sent to an anode furnace.
scrap material could be added. This is has now
Some operating data for the Mitsubishi pro- been solved [243]. With a smelting capacity of
cess (Naoshima Smelter, Japan) are summarized about 2000 t/d of copper concentrate, Naoshima
in the following: Smelter processes also about 40 000 t/a of cop-
per scrap from the market and additional anode
Commisioning date 1991 scrap from the refinery. Another problem is the
impurity behavior. Especially lead is a problem
S-furnace because of the calcium ferrite slag. If too much
Diameter inside brick, m 10
Number of lances 9 lead is in the feed, the copper anodes are too rich
Concentrate throughput, t/d 2050 in lead for electrorefining. A comparison of the
Copper scrap, t/d 20
Blast, m3 /h (STP) 37 500
impurity behavior is given in Table 14.
O2 enrichment, % 49
Off-gas volume, m3 /h (STP) 39 000 Table 14. Impurity contributions to anodes (wt % of input)
SO2 in off-gas, % 29
Matte grade, % 68 Process Reverbatory/Peirce – Smith Mitsubishi

Slag-cleaning furnace Pb 8 – 13 15 – 19
Size, inside brick w × l × h, m 6 × 12.5 × 2 As 9 – 11 4–6
Number of electrodes 6 Sb 28 – 34 15 – 20
Residence time ca. 2 h Bi 14 – 26 15 – 25
Slag 0.6 % Cu Ni 45 – 50 67 – 75
Off-gas volume, m3 /h (STP) 50

Figure 26. Mitsubishi process
5.7.3. Kennecott/Outokumpu Flash
Converting Process
In the 1980s Kennecott announced the develop-
ment of their Solid Matte Converting (SMOC)
process [244]. This process is based on solidify-
ing the molten matte from the smelter, grinding,
and feeding the solid to an high-oxygen blast
converter. This process decouples the smelting
and converting steps and gives great flexibility.
Later on, it was developed with Outokumpu, and
for the converting step also a well-proven flash
furnace was chosen. In 1995 the process went
into operation at Garfield Smelter.
For matte smelting a flash furnace with a con-
centrate feed rate of about 140 t/h was built (oxy-
gen enrichment 65 – 75 %). The liquid matte
contains 68 – 70 % copper and is granulated in
water. In the second step the matte is milled and
then fed together with lime as flux material to
the flash converter, which operates with an oxy-
gen enrichment of 65 – 75 % O2 . The feed rate
of matte is about 60 t/h (up to max. 80 t/h) [245].
This furnace is constructed like the smelting fur-
nace. A blister copper and a calcium ferrite slag
with about 18 % copper (like in the Mitsubishi
process) is obtained. The slag is granulated and
fed back to the flash smelter.
The off-gases contain > 30 % SO2 and are
converted to sulfuric acid (input concentration of
14 % SO2 in the sulfuric acid plant). This process
has very low SO2 emissions of only 3.5 kg SO2
per tonne of copper, which is until now the low-
Copper 37
est in the world. This is achieved because it has
almost no fugitive emissions. The disadvantage
is that no scrap can be added to the converter.
5.8. Direct Blister Smelting
Normally copper extraction takes place in two
steps – concentrate smelting and matte convert-
ing – in which the chemical reactions are prin-
cipally the same: oxidation of Fe and S. It has
long been the aim to combine these processes
in a single step/reactor and minimize the en-
ergy consumption and operating cost. Today (ca.
2000) direct blister smelting is carried out at two
smelters (Glogow, Poland and Olympic Dam,
Australia) in a Outokumpu flash furnace. Be-
tween 1973 and 1975, Noranda also used their
reactor for blister smelting from concentrate, but
it was switched to matte smelting because of
impurity problems. Another proposal is the QS
process.
5.8.1. Blister Flash Smelting [246]
This process takes place in a conventional Out-
okumpu flash smelting furnace. Concentrate and
silica flux are fed with 60 – 85 % O2 blast to
the burner. The amount of O2 is just enough to
form blister copper. In practise, the particles in
the reaction shaft are somewhat over-oxidized
on the outside and incompletely oxidized on the
inside. In the molten bath layers the reaction is
38 Copper
completed to form blister copper and iron silica
slag. Formation of a layer of matte between blis-
ter and slag must be avoided, because otherwise
a pronounced foaming reaction could take place.
In both operations copper concentrates with
low iron content (e.g., chalcocite, bornite) are
processed to minimize slag production and cop-
per loss in the slag. The slag has a high cop-
per content (15 – 21 % Cu), mainly in oxidized
form, and has to be reduced in an electric fur-
nace (produces copper – iron – lead alloy [247])
or concentrated by grinding and flotation. Re-
duction in an electric furnace with addition of
coke takes about 12 h residence time. The fur-
nace is operated at higher temperatures than the
normal flash smelter (slag temperature 1300 ◦ C)
to obtain higher solubility of magnetite in the
slag and decrease the viscosity of the slag. The
blister copper contains 0.3 – 1 % S. At the Glo-
gow Smelter, the process has been in operation
since 1977 with a daily throughput of 1500 t of
concentrate. At Olympic Dam it has been oper-
ated since 1988 and was enlarged in 1998.
5.8.2. QS Process
The QS process, based on the QSL leadmaking
process, was invented by Queneau and Schuh-
mann in 1974 [109]. Blister copper is produced
from concentrate in a single vessel. The reactor
is similar to the Noranda reactor but has counter-
current flow of slag and matte. Gases are injected
from the bottom [248] of the vessel to oxidize
Fe and S and to reduce the copper content in the
slag (Figure 27). Although the process has fun-
damental and technical merits, it has not been
realized in a commercial plant.
5.9. Copper Recycling
Most copper (> 95 %) is used in metallic form,
as copper metal or copper alloys. Recycling of
copper and its alloys has been carried out since
ancient times. In 1997, 37 % of copper consump-
tion came from recycled copper. This low figure
could be explained by the long lifetime of cop-
per products (e.g., more than 30 years for copper
wire) and the much increased copper production
in the last 50 years. Virtually all products made
from copper can be recycled, and copper can be
recycled over and over again without losing its
chemical or physical properties.
The processes used for copper recycling de-
pend on the copper content of the secondary
raw material, its size distribution, and other con-
stituents (Table 15) [249], [250]. Three general
types can be defined:
Type
– 1: copper scrap (new and old scrap), used
for smelting and refining or direct smelting
for products. This type accounts for about
95 % of all recycled copper. The value of the
metal is much higher than its treatment costs.
Type
– 2: copper-containing special scrap such as
cables and printed circuit boards. Pretreat-
ment (e.g., cable comminution) is necessary
before smelting the copper. Another example
is copper in cars. Each car contains 10 – 30 kg
of Cu which must be separated from the iron.
The value of the material is in the range of
the overall treatment cost.
Type
– 3: copper-containing residues, for exam-
ple sludges from metal-plating industry. The
copper content of these materials is low. The
value of the copper is much lower than the
treatment cost of the material.
High-purity secondary copper material is
used for smelting and casting new products, and
no fire and/or electrolytic refining is necessary.
This is also true of pure alloy scrap, which is
used for fresh alloy. With increasing impurity
content, the material is fed to smelting and refin-
ing processes. The process steps and aggregates
of secondary smelters are generally similar to
those of primary production, but the secondary
raw material is usually metallic or oxidic [253].
Therefore, mainly reducing conditions are used
for secondary smelting. Often carbon in the form
of coke or natural gas is used.
For smelting metallic scrap, often shaft fur-
naces (Asarco type or Contimelt) are used. For
smelting oxidic materials, blast furnaces, elec-
tric furnaces, TBRCs, and Isasmelt furnaces are
used. In the TBRC both the smelting and the
converting step could be done. This saves en-
ergy in comparison with the blast furnace and
Peirce – Smith converter. In some cases electric
arc furnaces are used instead of the blast fur-
nace. The advantage is that this furnace produces
about 80 % less off-gas than the blast furnace.
This makes the capture easier and more efficient.

Figure 27. QS process
Table 15. Overview of different sorts of secondary copper sources
Type Material Cu content, %
1 mixed copper scrap 90 – 95
1 pure copper scrap 99
1 red brass scrap 75 – 85
2 shredder material 60 – 65
2 cable 40 – 50
2 electronic scrap 10 – 20
3 sludges 5 – 10
3 copper – iron material 10 – 20
3 drosses, ashes, slags 20 – 25
A typical flow sheet of a secondary smelter is
shown in Figure 28.
Many primary smelters treat scrap besides
their internal recycling materials like anode
scrap from the tankhouse or converter flue dusts.
Additional copper scrap bundles are fed to the
Peirce – Smith matte converter. The scrap cools
the converters and uses the energy from matte
oxidation for heating and melting.
Also electronic scrap such as printed circuit
boards is fed to copper matte converters (e.g.,
Norddeutsche Affinerie [251], [252]) or No-
randa reactors (e.g., Noranda). The copper and
the precious metals are captured and sent to sub-
sequent refining. The organic polymers are burnt
at the high temperatures, and water and CO2 are
formed; ceramics are slagged. Because of the
high temperature and the high SO2 content in
the off-gas, no dioxins are formed.
5.10. Hydrometallurgical Extraction
About 15 % of the primary copper production
in the western world, that is, about 1.8 × 106 t/a,
Copper 39
Source Recycling process
sheets, gutters, water boilers, heaters, converting, fire refining
wires, pipes
semi-finished products, wire, strip, melting and casting of semifinished
cuttings products
valves, taps, machine components, converting or alloy production
fittings, bearing boxes, car radiators
cars blast furnace, electric furnace, TBRC
buildings, cars shredder, firerefining
electronics converting, TBRC
electroplating blast furnace, Electric furnace
armatures, stators, rotors blast furnace, electric furnace, TBRC
foundries blast furnace, electric furnace, TBRC
results from sulfuric acid leaching of copper ore,
which is combined with solvent extraction and
electrowinning. Other proposed techniques like
ammonia leaching or hydrochloric acid leaching
have minor importance. They are mainly pro-
posed for treating concentrates. A typical flow
sheet of a sulfuric acid leaching operation is
shown in Figure 29.
Chemistry Of Sulfuric Acid Leaching
Processes. There are two chemically different
classes of copper minerals:
1) Oxidic or secondary minerals like malachite
and chrysocolla
2) Sulfidic or primary minerals like chalcopy-
rite and chalcocite
The sulfidic minerals are the most common in an
ore body. Oxidic minerals are often located on
the top of the ore body and are present in smaller
amounts.
Chemical reactions during extraction of cop-
per from primary and secondary minerals are as
follows:
40 Copper

Figure 28. Flow sheet of a secondary smelter

Figure 29. Sulfuric acid leaching of copper ores


Oxidic secondary copper minerals:
CuCO3 · Cu(OH)2 + 2 H2 SO4 −→
2 CuSO4 + 3 H2 O + CO2
Sulfidic primary copper minerals:
First step: generation of Fe3+ , which is the
oxidant for copper leaching, by bacteria.
Thiobacillus thiooxidans:
2 FeS2 + 7 O2 + 2 H2 O −→ 2 FeSO4 + 2 H2 SO4
Thiobacillus ferrooxidans:
2 FeSO4 + 0.5 O2 + H2 SO4 −→ 2 Fe3+ + 3 SO2−
4 + H2 O
Second step: attacking the chalcopyrite:
2 Fe2 (SO4 )3 + CuFeS2 + 3 O2 + H2 O −→
5 FeSO4 + CuSO4 + 2 H2 SO4
Secondary minerals are readily soluble in sulfu-
ric acid, and reaction times are typically short.
After several hours most of the copper is ex-
tracted, but sometimes the ore requires a few
weeks reaction time. Recovery of copper from
primary minerals is more difficult because the
sulfides are very stable, and apart from sul-
furic acid an oxidant is required as well. The
most important oxidant is Fe3+ , which is gener-
ated from the mineral chalcopyrite by bacteria-
assisted reactions with atmospheric oxygen. Al-
though these bacteria, which normally exist in
the mine water, speed up the process, very long
reaction times like months or years are still nec-
essary to extract most of the copper. The con-
sumption of sulfuric acid depends on the type of
copper mineral. The bacterial leaching process
produces sulfuric acid itself.
Industrial Leaching Processes. The copper
leaching techniques in practical use are listed in
Table 16.
The most important technique is heap leach-
ing. It is very common for oxidic copper ore. The
typical copper content is between 0.25 and 1 %.
The ore is crushed to 1 – 10 cm and stacked to
heaps 3 – 10 m high with an area of about 10 000
to 100 000 m2 . Dilute sulfuric acid is sprayed on
the top of the heap. The liquor trickles through
the material, copper is dissolved, and the copper-
bearing solution (1 – 5 g/L Cu) is collected at the
bottom of the heap. This copper solution is puri-
fied and enriched by solvent extraction. Copper
Copper 41
metal is generated by electrolysis of the enriched
solution. After several months (1 – 6), leaching
is stopped and a new heap is placed on the top
of the previous and leaching is begun again.
Data from a typical heap leaching plant are
shown in Table 17. To produce 54 000 t/a of cop-
per, 27 000 t ore per day must be treated.
Table 17. Typical data of heap and dump leaching operation
Heap leaching Dump leaching
Cu cathode production, t/a 54 000 6600
Leach ore composition chrysocolla 95 %
chalcopyrite, 3 %
chalcocite
Soluble Cu in ore, % 0.54 0.15
Total area under leach, m2 200 000 300 000
Tonnes of ore per day 27 000 55 000
Annual Cu recovery rate, % 90 20
Sulfuric acid consumption, 1.7 0
t/t Cu
The copper production of a typical dump-
leaching operation is much lower, for example.
6600 t/a. The feed material is very low grade sul-
fidic ore, and several years are required to extract
all the copper. The sulfuric acid consumption
depends on the mineralization of the copper ore
and the composition of the host rock. Typical
figures are in the range of 1 – 5 t of sulfuric acid
per tonne of copper product.
Minor methods are in situ leaching, tailings
leaching, and vat leaching. Vat leaching was
carried out in the past to produce a pregnant
leach solution with about 30 g/L Cu which was
directly suitable for electrowinning. This tech-
nique is replaced by heap leaching and SX. Agi-
tation leaching is used mainly to leach oxidic Cu
concentrates in Zaire and Zambia. Fine particles
are treated with strong sulfuric acid (ca. 60 g/L)
solution, and the reaction is complete after sev-
eral hours.
Other Leaching Processes. Mainly for the
leaching of sulfidic copper concentrates, many
processes have been developed.
The Arbiter/Escondida Process was devel-
oped for leaching mainly chalcocite concen-
trates. In ammonia solution, half of the copper
is extracted very quickly and CuS remains in the
residue.
Cu2 S + 2 NH3 + 2 NH+
4 + 0.5 O2 −→
CuS + [Cu(NH3 )4 ]2+ + H2 O
42 Copper
Table 16. Common techniques for sulfuric acid leaching of copper mine
Leaching technique Mineralization
Heap oxides, chalcocite
Dump chalcopyrite
In Situ all
Vat oxides
Agitation oxides (carbonates)
Tailings oxides (carbonates)
The reaction takes place in agitated vessels. The
copper complex solution is sent to a solvent ex-
traction and electrowinning plant. The residue
is sent to a flotation plant, where copper is en-
riched, and then fed to a smelter. This process
was operated at Escondida mine in Chile but at
present is shut down.
The Cuprex process uses iron(III) chloride
for the oxidation of copper from chalcopyrite:
CuFeS2 + 4 FeCl3 −→ CuCl2 + 5 FeCl2 + 2 S
A solvent extraction step gives pure CuCl2 so-
lution (ca. 100 g/L Cu), which is fed to a mem-
brane-divided electrowinning cell, where cop-
per powder is produced and in at the anode the
iron(II) chloride is oxidized to iron(III) chloride
and recycled to the leaching process. The pro-
cess has been tested in a 1 t/d pilot plant.
The Intec process is carried out in a
NaCl/NaBr solution at 80 – 85 ◦ C with CuCl2
as oxidant. Leaching is carried out in four steps;
gold is also leached in the last step. The residue
consists of Fe(O)OH and elemental sulfur.
4 CuFeS2 + 4 CuCl2 + 3 O2 + 2 H2 O −→
8 CuCl + 4 FeOOH + 8 S
The solution is cleaned by adding CaO and then
sent to a membrane electrolytic cell. At the cath-
ode copper is reduced to copper powder. At the
anode two reactions take place: oxidation of Cu+
to Cu2+ and oxidation of bromide ions to BrCl− .
This solution, which contains about 30 g/L Cu,
is sent back to the leaching reactor (step 4, Au
leaching).
Oxygen pressure leaching of chalcopyrite,
bornite, or chalcocite concentrates in sulfuric
acid under 8 bar oxygen pressure at 200 ◦ C gives
about 99 % copper recovery after a short reac-
tion time of only one hour. The dissolved copper
can be recovered by electrowinning. The leach
% Cu in ore Leaching time Estimated Cu production
(1998), T/A
0.25 – 1 several months to years 700 000
< 0.25 1 – 5 decades 50 000
> 0.5 decades 50 000
1–2 5 – 10 d 50 000
20 – 40 2–5h 200 000
0.25 – 1 1d 100 000
residue can be treated with cyanide for gold re-
covery. This process was tested in laboratory
scale. It might find use for impure concentrates
or concentrates high in precious metals.
Bacterial leaching of chalcopyrite concen-
trates (Bio COP) is developed since 1997 at
Codelco’s Chuquicamata mine. The sulfide con-
centrate is leached in stirred tanks at 65 – 85 ◦ C
assisted by special heat-resistant bacteria (bac-
teria mesofila). The process needs large amounts
of air/oxygen. The copper sulfate solution is fed
to a SX-plant and then to copper electrowinning.
A pilot plant will be built within the next 2 years.
Solvent Extraction. The pregnant leach so-
lutions from heap, dump, or in situ leaching
are too dilute in Cu (1 – 5 g/L) and too impure
for direct production of high-grade copper cath-
odes. Industrial copper winning requires elec-
trolytes with about 40 – 50 g/L copper. Copper
enrichment and purification, mainly to remove
iron, is done by solvent extraction. The dilute,
impure solution from the leaching operation is
mixed with an organic solution, which is based
on kerosene or petroleum and contains about
5 – 10 % of an extractant which is selective for
copper. The organic extractants used for the pro-
cess are salicylaldoximes and ketoximes (RH)
and commercially available as LIX (Henkel) or
MOC (Allied Signal). The copper ions are com-
plexed by these reagents and enter the organic
phase:
2 RH + CuSO4 −→ R2 Cu + H2 SO4
After mixing, the aqueous and organic phases
are separated by gravity (settler). In a second
step, copper is stripped from the organic phase
with more highly concentrated sulfuric acid so-
lution.
H2 SO4 + R2 Cu −→ 2 RH + CuSO4

Normally, the depleted solution from elec-
trowinning, which contains about 170 g/L
H2 SO4 and 35 g/l Cu, is used. It is enriched
with copper to about 50 g/L and sent to the elec-
trowinning cells. Depending on the composition
of the dilute solution from the leaching plant sev-
eral mixer/settler steps are needed for purifica-
tion of the copper.
Copper Electrowinning. The copper-
enriched sulfuric acid solution (ca. 40 – 50 g/L
Cu, 140 – 170 g/L H2 SO4 ) is sent to the elec-
trowinning cells, which are similar in construc-
tion to refining copper cells. Copper is depleted
at the cathode on stainless steel sheet (ISA Pro-
cess) or copper starters. The cathode reaction is
identical to the refining reaction:
Cu2+ + 2 e− −→ Cu E 0 = 0.34 V
The anode reaction is completely different. In-
ert anodes, mainly PbSnCa alloy, are used, and
oxygen is formed at the anode.
H2 O −→ 0.5 O2 + 2 H+ + 2 e− E 0 = 1.23 V
The electrical potential needed for copper
electrowinning is about 2 V, as opposed to
about 0.3 V for copper electrorefining. About
2000 kW h is required for depleting 1 t of cop-
per. The usual plating period is about 7 d, af-
ter which around one-third of the cathodes are
taken out of the cell by crane and immediately
replaced by fresh ones, in contrast to the refining
tankhouse, where all cathodes are removed. The
cathode replacement in the winning tankhouse
is performed without cutting off the electrical
power. This maintains a passivation layer on
the lead anode and minimizes contamination of
the copper with lead. In addition, the electrolyte
contains about 100 ppm cobalt to prevent corro-
sion of the anodes. The lead anodes have life-
times of up to 20 years. The current density in
electrowinning plants is about 200 – 300 A/m2 .
Modern electrowinning tankhouses have capac-
ities up to 200 000 t/a of cathode copper.
Economics of Copper Production by
L/SX/EW Processes Compared with copper
production in smelters, L/SX/EW processes
have lower production figures. But the argu-
ments for the L/SX/EW techniques are low in-
vestment costs and increased copper output ef-
ficiency of mines. Furthermore, copper can be
Copper 43
recovered from low-grade materials which are
unsuitable for smelters. With improvements in
solvent extraction and electrowinning technol-
ogy, the quality of the recovered copper has be-
come as good as that from classical refineries.
Leaching facilities are mostly located at the cop-
per mines. The disadvantage of leaching is that
it does not recover the precious metals.
Production figures (in 103 t/a) for L/SX/EW
copper by region in 1997 follow:
North America 567
Latin America 943
Oceania 49
Africa 65
Asia 4
Western Europe 2
The expected growth of western world copper
production and the contributions from smelters
and L/SX/EW operations is shown in Figure 30.
Copper production is expected to increase from
about 12 × 106 t/a in 1996 to about 14 × 106 t/a
in the year 2000. The biggest part of this growth
will come from L/SX/EW operations. Smelter
production will also increase, but there the next
step in capacity enlargement is expected after
2002.
Figure 30. World copper production statistics
Most of the increase in copper production by
leaching was accounted for by Latin America
(Figure 31). By 2002 or 2003, the production of
L/SX/EW copper is expected to have increased
by nearly a factor of three. Several new opera-
tions are scheduled for the near future.
44 Copper
Figure 31. Copper production by the L/SX/EW technique
6. Refining
Conventional refining comprises three stages:
(1) pyrometallurgical or fire refining, (2) elec-
trolytic refining, and (3) remelting of cathodes
and casting of shapes. Refining without elec-
trolysis is adequate if the fire-refined copper
has the necessary purity and if the content of
precious metals can be neglected. If extremely
high-purity copper is needed, zone melting or
repeated electrolysis of cathodes is used.
6.1. Pyrometallurgical Refining
Fire refining is applied to crude copper such
as blister copper from converters (ca. 97 –
99 wt % Cu), black copper from blast furnaces
(ca. 90 – 95 wt % Cu), cement copper from hy-
drometallurgical operations (ca. 85 – 90 wt %
Cu), anode scrap from electrolytic refining, and
high-grade copper scrap, chiefly unalloyed wire
scrap.
The refining of molten copper to anode cop-
per for electrolysis or commercial fire-refined
copper has the following functions:
1) Removing impurities by slagging and
volatilization, with the precious metals re-
maining entirely in the metallic copper
2) Reducing the sulfur content to ca.
0.0005 – 0.005 wt % by oxidation
3) Decreasing the oxygen content to
< 0.1 – 0.25 % by reduction (poling) to give
a flat surface as a result of the water-gas
equilibrium in molten copper
6.1.1. Discontinuous Fire Refining
Two furnace types are available for batch copper
refining, the older reverberatory furnace and the
more modern rotary furnace. The former, which
resembles smaller reverbs for matte smelting
from concentrates, has a capacity of 200 – 400 t
of copper per charge, can be fed with molten or
solid copper, and is used in secondary smelters.
Rotary furnaces hold up to 350 t of molten metal
per charge and are generally fed only with liq-
uid copper. This type of furnace is preferred by
primary smelters because the reduction is more
efficient. An extra melting furnace, e.g., anode
shaft type (Section 6.1.2), can be required for
remelting of solid materials (scrap and anode
rests).
Low-sulfur pulverized coal, fuel oil, natu-
ral gas, or reformed natural gas serve as fuel.
The refractory lining consists of basic bricks,
such as magnesite or the more spall-resistant
chrome – magnesite bricks.
After charging and possibly melting, oxida-
tion and reduction stages are carried out in se-
quence. At the beginning of the oxidation pe-
riod, air is blown into the melt, partly slagging
and partly volatilizing the impurities. During this
blowing step, a part of the copper is oxidized to
copper (I) oxide, which dissolves in the liquid
metal (Fig. 32). If the content of Cu2 O in cop-
per increases to ca. 10 wt % (corresponding to
1 wt % O), it acts as a selective oxidizing agent:
Cu2 S + 2 Cu2 O −→ 6 Cu + SO2
In practice, large amounts of SO2 are generated
so that this final stage of the oxidation period is
termed boiling. Reduction of the sulfur content
limits SO2 blisters in the solid copper.
The subsequent poling with wood is a
centuries-old method that is still employed in
older reverb plants. Large tree trunks (poles) of
beech, birch, eucalyptus, etc. are plunged un-
der the surface of the melt to generate reducing
gases and steam by dry distillation of the wood.
The escaping gas mixture reacts with copper (I)

oxide and mixes the molten bath [1, p. 441], [2,
p. 392].
This awkward operation has been largely dis-
placed by gas poling [143] in rotary furnaces:
natural gas (CH4 ), reformed gas (CO, H2 , and
N2 ), propane, or ammonia [144] is blown into
the copper melt through tuyeres. This process
has been introduced at most smelters in the
world.
Figure 32. Partial phase diagram of the Cu – Cu2 O system
The poling operation proceeds in two steps.
During tight poling, the remaining sulfur dioxide
from copper (I) sulfide is almost entirely flushed
out by the escaping gas, a sample of liquid cop-
per at the end of this stage solidifying without
blisters or cavities. Next comes the poling tough
pitch, which is necessary to reduce the copper (I)
oxide and achieve the required low oxygen con-
tent. High Cu2 O content in the solidified metal
causes brittleness and decreased strength; more-
over, Cu2 O disproportionates to copper metal
and copper(II) ions in sulfuric acid electrolytes,
which disturbs the electrolytic refining opera-
tion.
The final oxygen content in fire-refined tough
pitch copper must be 0.02 – 0.05 wt %; for an-
odes it can be 0.05 – 0.3 wt %. The fire-refining
process can be understood from the Cu – O sys-
tem [145] (see Fig. 32); the system Cu – O – S is
important in the oxidation period (see Fig. 5) and
Copper 45
the Cu – H – O system for the reduction or poling
period.
When a copper melt solidifies, a shrinkage
of ca. 5 vol % occurs, but a flat surface can be
achieved by careful control of the equilibrium
Cu2 O + H2
2 Cu + H2 O
The steam of micropores can compensate the
volume difference, and a flat set cast is obtained.
Surface and fracture of small samples of so-
lidified copper from the molten bath are ob-
served during the refining process to ascertain
the current state. It is also possible to measure
the oxygen content of the copper melt potentio-
metrically.
A special problem is the extremely high
copper content (up to ca. 40 wt % Cu, chiefly
as Cu2 O) in refining slags. Such products are
treated as high-grade oxidized copper ores.
6.1.2. Continuous Fire Refining
The two-stage Contimelt process for copper
melting and refining was developed in 1968 by
Norddeutsche Affinerie at Hamburg, in coop-
eration with Metallurgie Hoboken-Overpelt in
Olen, Belgium [147]. The first stage began op-
eration in 1979, and the complete process has
been operated since 1982 on a commercial scale.
The continuous operations are performed suc-
cessively in two units connected by launders.
First is the anode shaft furnace, where charg-
ing, melting, and oxidation of crude copper take
place. Second is the small drum-type furnace,
where poling and casting of anodes are carried
out. The oxygen content of copper from the an-
ode shaft furnace averages 0.6 %, with 0.15 %
after poling. A feature of the shaft furnace is the
additional equipment with oxygen burners for
regulating the composition of the furnace atmo-
sphere and the overheating of copper. In com-
parison with conventional fire refining, the Con-
timelt process provides savings in energy and
labor.
6.1.3. Casting of Anodes
The conventional method of producing anodes is
the discontinuous casting on casting wheel ma-
chines. The pure copper molds must be sprayed
46 Copper

with a slurry that prevents the sticking of so- 6.2.1. Principles [149], [150]
lidified anodes; baryte, alumina, or silica flour
are suitable. (Calcium-containing material is Several possible half-reactions can occur at the
not suitable because it forms gypsum, which is electrodes.
partially soluble in the electrolyte.) The cast-
ing rate can reach 100 t/h. The anode weights Anode reactions Cathode reactions Standard electrode
potential
vary between 250 and 450 kg, depending on E ◦ (25 ◦ C), V
the refinery. Anodes from modern plants usu-
ally have the following dimensions: 0.9 – 1.1 m Cu Cu2+ + 2 e− 0.337
−→ Cu2+ + 2 e− −→ Cu
long; 0.9 – 1.0 m wide; and 3.5 – 6.0 cm thick. Cu Cu+ + e− 0.521
They weigh 300 – 450 kg. Economic considera- −→ Cu+ + e− −→ Cu
tions call for anodes of nearly the same weight Cu+ −→ Cu2+ + eCu
− 2+
+ e− 0.153
−→ Cu+
within a plant; therefore, discontinuous casting
is best controlled by electronic systems.
Secondary reactions occur in the electrolyte:
Contilanod Process. The Contilanod pro-
2 Cu+ −→ Cu2+ + Cu (disproportionation)
cess, developed by Metallurgie Hoboken-
Overpelt in Olen, Belgium, produces uniform
2 Cu+ + 2 H+ + 0.5 O2 −→ 2 Cu2+ + H2 O (air oxidation)
anodes by using the continuous Hazelett twin-
belt casting system [148]. The continuous cast
strip of anode copper formed between two belts Cu2 O + 2 H+ −→ 2 Cu+ + H2 O (dissolution of Cu2 O)
and damblock chains is 1 m wide and 1.5 – 6 cm Oxidation by air and disproportionation of cop-
thick; special cutting equipment separates the per (I) ions yield a surplus of copper (II) ions in
strip into individual anodes 1 m long. Some re- the electrolyte. The copper metal powder formed
fining plants use this method, e.g., White Pine, by the disproportionation of Cu+ contributes to
Michigan, United States; Kidd Creek, Timmins, the accumulation of the anode slime.
Canada. The advantage of this system is the uni- The electrochemical equivalent of copper de-
formity of the anodes and the high degree of pends on the oxidation state of the copper:
automation. But in comparison to the mold-on-
wheel technique, the Hazelett caster has some-
Species g A−1 h−1 mg/L
what higher maintenance costs.
2+
Cu 1.185 0.3294
Cu+ 2.371 0.6588

6.2. Electrolytic Refining

About 80 % of the world copper production is
refined by electrolysis. This includes all primary
copper and much secondary copper. This treat-
ment yields copper with high electrical conduc-
tivity and provides for separation of valuable im-
purities, especially the precious metals.
The basic patent, GB 2838, for galvanic de-
position of metals was awarded to J. B. Elk-
ington in 1865. The most important technical
problems were solved by E. Wohlwill at the
Norddeutsche Affinerie in Hamburg, Germany,
in 1876, and this method has been used ever
since. The first electrolytic copper refinery in the
United States was operated from 1883 to 1918 by
the Balbach Smelting and Refining Co., Newark,
New Jersey.
The greater electrochemical equivalent of
copper (I) suggests the use of solutions of cop-
per (I) ions instead of copper (II) ions. However,
this concept has not been put into practice be-
cause of enormous industrial difficulties [151].
The two most important electrical parame-
ters in electrolytic copper refining operations are
the cell voltage and the current density. The cell
voltage, which usually ranges between 0.25 and
0.3 V, is determined by several factors:
1) Ohmic resistance of the electrolyte, depend-
ing on composition, temperature, electrode
distance, and cell construction
2) Polarization, especially concentration polar-
ization of electrodes, which depends on the
rate of electrolyte circulation

3) Overpotential because of organic additives
(e.g., an inhibitor for achieving uniform elec-
trocrystallization of copper)
4) Voltage loss in the circuit
5) Anode passivity, which may occur at high
current densities
The interaction of these effects is difficult to
predict. At any particular electrolytic facility, a
continuing effort is made to optimize parameters
that affect the cell voltage. The voltage loss in the
conductors and contacts is minimized by good
plant design and use of special contacts (Bal-
timore grooves, Whitehead contacts, wet con-
tacts, etc.).
The second important parameter is the ca-
thodic current density. With increasing current
density the production of copper increases and
the current efficiency decreases because the
cathode potential depends on the current den-
sity.
Impurities. The behavior of impurities de-
pends on their position in the electrochemical
series: elements more noble than copper are in-
soluble, while less noble ones dissolve in or re-
act with the electrolyte. For that reason, the an-
ode material is distributed by electrolysis among
three phases: cathode copper, electrolyte, and
anode slime (Table 18) [152]. Table 19 lists the
fractions of anode elements that enter residues
and electrolyte.
Copper Cathodes. Cathode copper is pro-
duced currently in a purity between 99.97 and
99.99 %. Silver can be deposited in traces; how-
ever, this can be avoided by precipitating the
silver from the electrolyte with chloride ion.
Other impurities, such as suspended slime or
droplets of the electrolyte, may be mechanically
occluded. The following measures are taken to
produce copper of high purity:
1) Maintenance of the optimum current density,
to prevent cathodic deposition of other ele-
ments (e.g., arsenic)
2) Addition of organic inhibitors to avoid the
formation of nodules on the cathode surface
3) Removal of impurities such as arsenic, anti-
mony, and bismuth from the electrolyte by
adsorption or chemisorption
Copper 47
4) Prevention or elimination of suspended
slimes by regulating the electrolyte flow and
occasionally filtering it.
Electrolyte. The composition of copper elec-
trolytes from various plants is generally simi-
lar: ca. 35 – 45 g of copper and 150 – 220 g of
sulfuric acid per liter at an operating tempera-
ture of 55 – 65 ◦ C (see Table 14). As a result of
secondary reactions during electrolysis, the con-
centration of copper (II) ions increases slowly;
therefore, this copper surplus must be recovered
by cathodic deposition in a few (ca. 2 %) liber-
ator cells equipped with insoluble anodes, usu-
ally of antimonial lead. Soluble impurities, such
as iron, cobalt, zinc, manganese, most of the
nickel, and some arsenic and antimony, are also
enriched in the electrolyte.
The upper limits of impurity content are ca.
10 g/L for arsenic and 20 – 25 g/L for nickel.
Part of the electrolyte is withdrawn continuously
from the circuit for purification, and the volume
is compensated by adding sulfuric acid and cath-
ode wash water. There are two methods of pu-
rification. In the first, the solution can be com-
pletely decopperized in a system of special lib-
erator cells with insoluble anodes; arsenic and
antimony are almost completely deposited and
returned to pyrometallurgical operations. The
electrolyte is then concentrated by vacuum evap-
oration to yield concentrated sulfuric acid and
crude nickel sulfate, from which pure nickel sul-
fate or nickel metal can be produced.
The second method of purification is by pro-
ducing copper sulfate. For this purpose, the sul-
furic acid is usually neutralized by addition of
copper shot in the presence of air. The copper
sulfate is obtained by crystallization, and the
mother liquor is cemented with iron scrap.
Anode Slimes [153], [154]. The content of
insoluble substances is < 1 % of the anode
weight, and they collect on the bottom of cells
as anode slime. They contain precious metals
(silver, gold, and platinum); selenides and tel-
lurides of copper and silver; lead sulfate; stan-
nic [tin (IV)] oxide hydrate; and complex com-
pounds of arsenic, antimony, and bismuth (the
undesired floating slimes). The main component
is copper. In addition, gypsum and silica, alu-
mina, or baryte from anode casting are present.
48 Copper
Table 18. Industrial range of copper anode and cathode compositions Table 19. Fractions of anode elements entering residues and elec-
trolyte
Element Anodes (%) Cathodes (%)
Metal Percentage into anode Percentage into
Cu 99 – 99.8 99.99 + (excluding residues electrolyte
oxygen)
O 0.1 – 0.2 not determined Cu < 0.2 > 99.8
Ag 0.01 – 0.5 0.0005 – 0.002 Au 99 <1
S 0.0005 – 0.005 0.0004 – 0.001 Ag 98 2
Ni 0.002 – 0.7 trace – 0.0003 Se and Te 98 2
Pb trace – 0.5 trace – 0.0004 Pb 98 2
Fe 0.001 – 0.006 0.0001 – 0.0002 Sb 50 50
Sb trace – 0.1 trace – 0.0002 As 30 70
As trace – 0.2 trace – 0.0002 Co 5 95
Se trace – 0.2 trace – 0.0001 Ni 5 95
Te trace – 0.03 trace – 0.0001 Fe 0 ca. 100
Bi trace – 0.03 trace – 0.0001 Zn 0 ca. 100
Au trace – 0.004 trace Bi ∗

∗ Dissolves up to about 0.15 – 0.2 kg m3 in electrolyte, then

forms slimes.

The distribution of the elements (in %) varies different starting cathode sheets are used. The
over wide ranges: conventional system uses thin copper sheets,
while the modern systems (ISA developed by
copper 20 – 50
nickel 0.5 – 2 Copper Refineries [167], Australia and Kidd de-
lead 5 – 10 veloped by Kidd Creek Divison, Falconbridge,
arsenic 0.5 – 5
antimony 0.5 – 5
Canada) utilize permanent stainless steel cath-
bismuth 0.5 – 2 ode sheets. The cathode copper is stripped
selenium 5 – 20 mechanically from the steel sheets, which are
tellurium 1–4
silver
25 used again, while copper starting sheets have to
gold
4 be prepared for each cathode. The advantages
of the permanent cathode systems are high de-
Although the separation techniques differ gree of automation, very low personnel costs,
greatly from plant to plant, anode slimes are gen- higher specific production rate, and higher cath-
erally treated as follows: ode quality (lower content of impurities, e.g.,
lead).
1) Oxidizing leaching of copper with dilute sul-
furic acid Cells and Operation. The cells or elec-
2) Recovery of selenium and tellurium by py- trolytic tanks are constructed of reinforced con-
rometallurgical or hydrometallurgical meth- crete lined with antimonial lead sheet or with
ods flexible poly(vinyl chloride) or of polymer con-
3) Removal of detrimental elements and pro- crete without a lining. The cells are rectangular,
duction of silver alloy (Doré bullion) 3.5 – 6 m long, 0.8 – 1.2 m wide and 1.2 – 1.5 m
4) Separation of precious metals by electrolysis deep. Copper anodes and starting sheet cathodes
(silver and gold) and fractional precipitation are suspended alternately in the cells with pre-
(platinum metals) cise spacing by overhead crane. In most refiner-
The greatest part of the world selenium pro- ies the anodes are prepared (pressed to make
duction comes from processing copper anode them uniformly flat and weighed) before they
slimes. are inserted into the cells. Commercial cells con-
tain between 40 and 60 electrodes of each type.
The distance between the surfaces of the two ad-
6.2.2. Practice of Electrorefining [155–157] jacent electrodes should be small (about 2 cm)
to avoid voltage loss, but not so small that the
Electrorefining is carried out in large tankhouses deposited copper is contaminated with anode
with capacities up to 500 000 t/a of pure cathode slime. Electrolyte is circulated through each cell
copper. Today two techniques with principally at ca. 0.02 m3 /min. At this flow rate the elec-

trolyte in one cell is exchanged every 5 – 6 h,
which is important for removing impurities from
the cell.
The anodes remain in the cell for 20 – 28 d.
During this time the cathodes are usually
changed two or three times, so that their weight
is only 60 – 160 kg. The cathodes are removed
by crane and the electrolyte on their surface is
washed off with hot water. In tankhouses which
use stainless steel sheets, the plated copper is
stripped mechanically (automatic stripping ma-
chine) from both sides of the blank. In conven-
tional tankhouses copper starter sheets are pre-
pared by electrodeposition of copper on titanium
sheets (< 1 mm, about 1 d) in special stripper
cells. Then the copper sheets are attached to
rolled copper support bars for hanging in the
cells. This process is partly mechanized [164].
About 15 % of the anode is not dissolved dur-
ing the refining process. This anode scrap is re-
cycled to the smelter (converter or shaft furnace).
The anode slime of the complete cycle is drained,
filtered, washed, and sent to the precious metal
plant. Part of the electrolyte is removed continu-
ously from the circulation system for purifying.
The sulfuric acid is sent back to the tankhouse.
Electrical System. The anodes and cathodes
in a cell are connected in parallel. The cells are
connected in series to form sections of 20 to 40
cells. Each section can be isolated electrically
for inserting or removing anodes or cathodes.
For example, 12 sections are connected with one
silicon controlled rectifier for current input. To-
tal electrical current through the cell is between
10 000 and 40 000 A. Electrical densities of up to
40 kA/m2 are used in ISA tankhouses today. To
obtain a high current efficiency of 92 – 98 %, the
bath and section voltages are monitored [254],
[255], and the temperature of the cells is mea-
sured by infrared techniques (from the crane). In
this way short circuits, caused, for example, by
the growth of copper nodules can be quickly de-
tected and corrected. The energy consumption
of electrorefining per tonne of plated copper is
about 260 – 280 kW h.
Electrocrystallization [163]. The structure
of an electrodeposited cathode surface can be
influenced by adsorption of molecules on the
crystallites. The addition of colloids or special
organic compounds improves cathode quality by
Copper 49
yielding an evenly grained copper deposition.
Important surface-active additives, or inhibitors,
are bone glue, gelatin, avitone A (sulfonated
aliphatic hydrocarbons), goulac, or bindarene
(sulfonated wood fibers). Effective substances
with definite composition are thiourea and its
derivatives and other sulfur – nitrogen com-
pounds. These inhibitors, mostly in combina-
tion, are added to the electrolyte in extremely
small amounts, although more is added at higher
current density. Inhibitors increase the voltage
and, therefore, the energy consumption. Several
refineries automatically control their reagent ad-
dition rates by measuring glue and thiourea, for
example, with the CollaMat [254–256] system.
This stabilizes refinery operation and optimizes
the process (lower energy consumption).
Special Developments. Jumbo tanks instead
of conventional cells, first installed in 1972 at
Onahama Tankhouse, Japan [165]. The jumbo
tanks have about 20 times the volume of con-
ventional cells. The electrolyte flows parallel to
the electrode surface, in contrast to conventional
cells. A newer installation of jumbo tanks is the
Kidd Creek tankhouse in Canada.
To overcome anodic passivation caused by
high current density and impure anodes a peri-
odic current reversal system (PCR) [166] was
developed. Optimum reversal conditions seem
to be 20 units forward time and 1 unit reverse
time [257]. This system has been adopted in
some refineries, but due to the extra energy costs
it is not widely used.
6.3. Melting and Casting
Copper cathodes must be remelted and cast to
shapes because the structure of copper formed
by electrocrystallization is not suitable for work-
ing to semifinished products. Cathodes are
remelted in several types of special furnaces that
perform the tasks of melting, postrefining (if
necessary), holding, and casting. Casting can be
carried out by the older discontinuous methods
or by modern continuous casting.
50 Copper
6.3.1. Remelting of Cathodes
There are various kinds of furnaces that use ei-
ther fossil fuels (coal, coke, fuel oil, natural gas,
or reformed natural gas) or electric energy:
Small coke-fired crucible furnaces
Gas- or oil-fired rotary furnaces
Large hearth furnaces (reverbs)
Electric-arc furnaces
Low-frequency induction furnaces
Cathode shaft furnaces (e.g., ASARCO type)
Copper ready for pouring must be nearly free
of sulfur, at most 10−3 % (10 ppm) S, because a
higher content affects detrimentally the mechan-
ical properties of the metal.
In practice, copper is treated in two ways:
1) After melting cathodes with sulfur-
containing fuels, the copper melt must be
fire-refined like blister copper, by oxidation
and poling. This is the case when hearth
furnaces are employed for casting.
2) Use of electric power or sulfur-free fuels al-
lows the use of continuous units, such as in-
duction or ASARCO furnaces.
The ASARCO shaft furnace, constructed by
American Smelting and Refining Co. [168],
[169], has a cylindrical shaft consisting of a steel
jacket with a brick lining. Cathodes are charged
near the top, and the combustion gases ascend
in countercurrent flow from groups of burners;
the liquid metal is collected in a holding furnace.
Apart from its effectiveness and high productiv-
ity, a distinct advantage is the maintenance of a
constant, slightly reducing atmosphere by auto-
matic control. The largest types (1.8 m diameter
and 8 m high) can have a throughput up to 80 t/h.
Worldwide ca. 200 units are in operation.
6.3.2. Discontinuous Casting
The discontinuous casting of various shapes
on horizontal casting wheels with open ingot
molds, analogous to the casting of anodes, was
formerly the most important casting method. It is
being replaced by continuous casting processes.
6.3.3. Continuous Casting
Since the end of World War II, several contin-
uous casting methods have been developed. A
comprehensive synopsis, including patents, has
been published [171].
Continuous casting has several technological
and economic advantages over the older casting
processes, such as excellent surface quality, uni-
form grain structure without blisters and shrink-
age cavities, and energy savings.
Molten copper flows continuously into a rel-
atively short water-cooled chill, usually lined
with graphite and open at both top and bottom.
The solidifying metal itself forms the lower clo-
sure. The shape is steadily withdrawn by clamp-
ing rolls and cooled by spraying with water.
There are three main continuously cast
shapes: circular billets with a diameter up to
500 mm (for extrusion presses or tube rolling
mills), square bars, and rectangular cakes with
cross sections up to 1300 × 200 mm (for rolling
to sheets and strips). Seamless tubes and other
hollow shapes are occasionally produced. Con-
tinuous casting shapes are automatically sawn
off by flying saws when they reach the required
lengths (up to 7.5 m). In semicontinuous casting,
the process must be interrupted, but the shapes
can be up to ca. 12 m long.
The kind of chill is generally independent of
the furnace: the liquid metal stream free-falls
into the chill (e.g., Junghans system), or the less
frequent fixed connection of chill with the fur-
nace (e.g., ASARCO casting system).
Other methods employ a joint moving in uni-
son with the solidifying metal and a mold with
traveling parts forming a gap of the required
cross section. (An example is the Hazelett pro-
cess employed for continuous casting of anodes.
Section 6.1.3.) Such casting methods are par-
ticularly suitable for continuous production of
shapes with a small cross section. Section 6.3.4.
6.3.4. Continuous Rod Casting and Rolling
The continuous production of cast and rolled
wire rod [172], [173] involves considerable en-
ergy savings because the solidified hot metal can
be rolled immediately. Several plants use such a
direct process starting from molten electrolytic
tough-pitch copper. Worldwide >100 plants are
in operation, using the following systems:

1) Properzi process [174]. The first continuous
copper rod caster was constructed in 1960
following developments for other nonferrous
metals. It operates on the wheel – belt casting
principle, i.e., casting into the gap between
the periphery of the casting wheel and the
closing steel belt. About ten plants are in op-
eration with a capacity up to 30 t/h.
2) Southwire process [175]. Started in 1963 as a
further development of the wheel – belt cast-
ing principle with capacity up to ca. 50 t/h,
the Southwire process directly introduces
the continuous cast bar into the rolling mill
(Fig. 33). After rolling, the rod, which is ox-
idized on the surface, is continuously treated
by pickling with dilute sulfuric acid or alco-
hols, water or steam rinsing, and wax coating.
The saleable product (8 – 20 mm diameter) is
formed into “coils” of up to 10 t, which are
packaged. About 30 plants exist at present.
3) Secor process [177]. Only two factories
(Australia and Spain) use this modified
wheel – belt casting concept, dating from
1975, with a capacity up to ca. 10 t/h.
4) Contirod or Krupp – Hazelett process [178].
As a variant of the Hazelett twin-belt pro-
cess similar to the Contilanod process (Sec-
tion 6.1.3.), the continuous cast bar solidifies
between two belts and damblock chains and
is directly moved to the rolling mill (Fig. 33).
Metallurgie Hoboken-Overpelt, Belgium,
developed this system in the 1960s; the ca-
pacity of the largest units is ca. 50 t/h. At
present about 20 plants are operated.
5) General Electric dip forming process [179].
A process based on the “candlestick” prin-
ciple has been operated since about 1970. A
copper core rod is pulled upward through liq-
uid copper so that its diameter increases; the
thickened rod moves immediately to rolling.
Oxygen-free copper can be produced by us-
ing a reducing atmosphere. The capacity is
ca. 10 t/h. Nearly 20 plants exist at present.
6) Outokumpu up-cast process [180]. A new
upward casting system developed in 1969
draws copper upward through a vertical die
cooler with a cooled graphite mouthpiece
dipping into the melt. The caster, compris-
ing 8 or 12 strands, yields oxygen-free cop-
per at the rate of ca. 2 t/h per line. Because of
the small cross section (8 – 25 mm diameter),
Copper 51
hot rolling is not required. Approximately 40
plants are in operation.
6.4. Copper Powder
Copper and copper-alloy powders are required
for products prepared by powder metallurgical
techniques, including friction materials, carbon
brushes, self-lubricating bronze bearings, spe-
cial filters, and catalysts and other sintered com-
ponents.
The principal methods for producing cop-
per powders are electrolytic deposition at high
current densities and the atomization of molten
metal, the latter more for copper-alloy powders.
Copper powders are also formed by cementa-
tion or by pressurized precipitation from aque-
ous solutions, but such precipitates are of little
commercial interest.
Atomizing is done by spraying a melt into
a pressurized air or water flow. Various grain
shapes are formed, depending on the cooling
rate and on additives that change the surface
tension. Additives that decrease surface tension,
e.g., magnesium, form irregular powders; those
that increase it, e.g., lead or phosphorus, yield
globular particles. Spongy powders can be ob-
tained by reduction of oxidized copper powders
with hydrogen.
Electrolytically deposited powder particles
have dendritic shape; a typical flow sheet is
shown in Figure 34. For this purpose electrolysis
is used as a shaping process rather than for refin-
ing because high-purity copper cathodes are the
anodes. The main parameters of powder elec-
trolysis are, as Figure 35 shows, the following
[181]:
Cathodic current density
Electrolyte temperature
Concentration of copper (II) ions
Concentration of chloride ions
Varying these factors markedly change particle
shapes and apparent densities.
Anodic and cathodic current densities dif-
fer. The former is normally 300 – 600 A/m2 , and
the latter is 2000 – 4000 A/m2 , which is 10 – 20
times higher than the cathodic values in conven-
tional electrolytic copper refining. This effect is
obtained by using copper rod cathodes and plate-
like anodes. The energy consumption in powder
52 Copper
Figure 33. Scheme of continuous rod casting and rolling [176]
A) Southwire process; B) Contirod process.
a) Melting furnace (ASARCO); b) Holding furnace; c) Wheel; d) Tundish; e) Steel band; f) Continuously cast copper bar;
g) Preliminary rolling mill train; h) Finishing rolling mill train; i) Pickler; j) Coiler; k) Casting receptacle; l) Casting canal;
m) Stationary edge dams; n) Middle rolling mill train
electrolysis averages nearly 2 kWh kg−1 . The
powders are generally posttreated for various
purposes. Electrolytic copper powders are char-
acterized by dendritic particle shape, high purity,
low oxygen content, favorable resistance to ox-
idation, and good green strength.
During the last 5 years the electrowinning
technology to produce copper powder was de-
veloped to commercial scale. By using pregnant
leach solution from ore leaching operation and
subsequent solvent extraction and electrowin-
ning in specially designed cells, it is possible
to produce dendritic shape copper powder with
well defined parameters like particle size [258].
6.5. Copper Grades and
Standardization
The three main grades of refined copper are (1)
tough-pitch copper, (2) deoxidized copper, and
(3) oxygen-free copper.
Without regard to the method of refining,
tough-pitch copper normally contains 0.02 –
0.04 wt % O (as Cu2 O) and ca. 0.01 wt % total of
other impurities. This grade is easily worked and
has an electrical conductivity of  100 % IACS,
but it is unsuitable for welding and brazing be-
cause of the danger of hydrogen embrittlement.
About 80 % of the world production of refined
copper is tough pitch, mostly electrolytic tough-
pitch copper (ETP).
Deoxidized copper, with no oxygen content
is produced by addition of nonmetallic or metal-
lic reducing agents, usually copper phosphide.
As a result of the absence of oxygen, hydrogen
embrittlement cannot occur, and such copper is
well suited for welding and brazing. The con-
tent of residual phosphorus, however, increases
the electrical resistivity. Deoxidized copper with
low residual phosphorus (DLP, ca. 0.005 % P) is
required if the metal is to be used as a conduc-
tor. Copper with high residual phosphorus (DHP,

Figure 34. Flow sheet for electrolytic copper powder pro-
duction [181]
ca. 0.04 % P) can be employed for nonelectrical
purposes.
Oxygen-free (OF) copper is a special qual-
ity produced by keeping oxygen away from the
copper melt in a controlled atmosphere. Cop-
per of this type with an oxygen content less
than 0.001 wt %, is suited for purposes requiring
weldability and high electrical conductivity, es-
pecially electronics. OFHC, oxygen-free high-
conductivity copper, is internationally known.
Standardization [14], [182], [183]. Most
industrial countries have established standards
for copper; these national specifications include
detailed specifications for chemical composi-
tion, physical properties, and geometrical di-
Copper 53
Figure 35. Apparent density of electrolytic copper powder
as a function of four electrolysis parameters [181]
Other conditions: A) Cu 6 g/L, no Cl, 60 ◦ C; B) Cu 17 g/L,
no Cl, 3600 A/m2 ; C) no Cl, 50 ◦ C, 3600 A/m2 ; D) Cu
13 g/L, 50 ◦ C, 3600 A/m2
mensions, but differences exist. Table 20 indi-
cates the rough equivalent between international
and European specifications for the most impor-
tant copper properties.
6.6. Quality Control and Analysis
Tests for quality control of copper are carried out
on samples of both refinery shapes and semifin-
ished products. There is need to standardize the
testing methods, but currently only some of them
are fixed in national specifications. The most im-
portant tests are the measurement of electrical
conductivity, mechanical properties, and qual-
ity of the metal surface.
54 Copper
Table 20. Comparison of international and selected national standards

International European EN Materials Composition, % Electric Remarks

ISO R 1337 prEN 1977 Number conductivity, %
prEN 1978 prEN 1412 IACS

Cu min O2 max P min P max

Cu-CATH1 Cu-CATH1 CR001A 99.99 higher grade

cathodes
Cu-CATH2 Cu-CATH2 CR002A 99.9 standard cathodes
Cu-ETP1 Cu-ETP1 CR/CW003A 99.9 0.04 101 electrolytically
refined, tough pitch
copper
Cu-OF1 Cu-OF1 CW007A 99.99 101 oxygen-free copper
Copper not produced from Cu-CATH-1 Cathodes:
Cu-ETP Cu-ETP CR/CW004A 99.99 0.04 100 electrolytically
refined tough pitch
copper
Cu-FRHC Cu-FRHC CR/CW005A 99.99 0.04 100 fire-refined tough
pitch copper
Cu-OF Cu-OF CR/CW008A 99.95 100 oxygen-free copper
Cu-FRTP Cu-FRTP CR/CW006A 99.9 0.1 fire-refined copper
Phosphor containing Copper:
Cu-PHC Cu-PHC CR/CW020A 99.95 0.001 0.006 100
Cu-HCP Cu-HCP CR/CW021A 99.95 0.002 0.007 98.3
Cu-DLP Cu-DLP CR/CW023A 99.9 0.005 0.013 deoxidized copper
with low P content
Cu-DHP Cu-DHP CR/CW024A 99.9 0.015 0.04 deoxidized copper
with high P content

The electrical conductivity is very sensi-
tive to impurities and crystal lattice imperfec-
tions. Mechanical tests measure hardness, ten-
sile strength, elongation at failure, and torsional
fatigue strength. The spiral elongation test [184]
is a complicated test method that assesses the pu-
rity and the mechanical behavior of the sample.
Defects on the surface and subsurface can occur
in various forms, e.g., folds, splashes, cracks,
inclusions, and voids. The voids are caused by
gas porosity, shrinkage porosity, and shrinkage
cavities.
Nondestructive testing procedures, such as
radiography, ultrasonic examination, or the
eddy-current technique can be used. Metallo-
graphic methods (polishing and etching) give
information by microscopic examination.
Analytical methods are of interest for de-
termining the impurity level of copper prod-
ucts. Both wet chemical procedures and phys-
icochemical procedures, such as atomic ab-
sorption spectrometry, optical emission spec-
troscopy, and X-ray fluorescence spectroscopy,
are employed, the latter essentially for quick
analysis of solid and liquid co- and byproducts
[185], [186]. The classical analytical methods
are gradually being superseded by the modern
automatic instrumental techniques. It is espe-
cially important to analyze the oxygen content,
and one effective modernized method is avail-
able, hot extraction, i.e., melting a copper sam-
ple in a small graphite crucible and determining
the CO formed by IR absorption spectroscopy.
7. Processing and Uses
The pure metal produced in refineries or remelt-
ing plants is manufactured into semifabricated
products.
7.1. Working Processes
Usually copper is treated initially by noncutting,
shaping processes to obtain semifinished prod-
ucts or “semis”. These processes are subdivided
into hot working, cold working and, if necessary,
process annealing.
Hot working means plastic forming above the
recrystallization temperature. Generally copper
is preheated to 800 – 900 ◦ C, and the subsequent
hot forming is finished at ca. 400 ◦ C. Cast bars
from modern combined continuous casting/rod-
rolling systems already have sufficient temper-
ature, thus saving thermal energy. After cool-
ing, the hot-worked copper is soft copper. Its
 Copper 55

mechanical and electrical properties are scarcely drawing. Many products of varying size are
changed, but its density has increased to nearly fabricated by modern variants of the extrusion
8.9 g/cm3 . process [187]. The fabrication of tubes is also
The next step is cold working, which involves quite diverse [188]. The most widely used work-
plastic forming below the recrystallization tem- ing processes are compiled in Table 21.
perature. In practice, the operation is done at
room temperature. Unlike hot working, this pro-
cedure entails an essential strain hardening of 7.2. Other Fabricating Methods
the metal by increasing the number of lattice
defects; however, simultaneously formed lattice In many cases, machining operations are re-
voids cause a considerable decrease of electrical quired, e.g., cutting, turning, planing, drilling,
and thermal conductivity. After cold working, and sawing. However, these are more important
the metal is hard copper. for copper alloys than for pure copper because
Process annealing is a heat treatment that is of copper’s tendency to gum. Noncontinuous
necessary if the hardened copper must be soft- casting processes are likewise more suitable for
ened again, either for continued working or for copper alloys because copper has a disadvanta-
producing (soft) copper with high electrical con- geous coolability. These include sand mold cast-
ductivity. Special furnaces are used for the pur- ing, permanent mold casting, gravity die cast-
pose of steady heating and cooling of the metal – ing, pressure die casting, and centrifugal cast-
often in a nonoxidizing atmosphere. To achieve ing. Continuous or semicontinuous casting pro-
the intended microstructural change, the recrys- cesses, however, are well-suited for pure copper.
tallization temperature of 200 – 300 ◦ C must be Galvanoplasty is an electrolytic operation for
exceeded; in practice, the metal is heated to manufacturing complicated objects that require
400 – 500 ◦ C for accelerated recrystallization. high precision and flawless surfaces such as hol-
Copper products with exactly defined properties low bodies, disk matrices, and electrotypes. A
can be obtained if all annealing conditions are special galvanic method is copper plating, which
carefully controlled. involves electrolytic deposition of a thin layer of
copper on another metal either for surface pro-
Table 21. Important fabricating processes for copper products tection or as a base layer for electroplating with
Refinery Hot-working Cold- Semi-finished another metal (→ Electrochemical and Chemi-
shapes process working products cal Deposition).
process
Powder-metallurgical techniques are used
Cakes hot rolling → cold rolling sheets/strip primarily for the mass production of small
Rod −→wire wires pieces, especially intricate forms such as elec-
drawing
Billets extruding → cold rods/sections trotechnical and mechanical structural parts. The
drawing metal powders are first compacted by pressure
Billets extruding → cold tubes/pipes
drawing
and then sintered in a controlled atmosphere.
The copper powder is often mixed with other
or or powdered metals, including those that do not
hot rotary → cold pilger
piercing rolling
form common copper alloys (→ Powder Met-
allurgy and Sintered Materials).
There are other important fabricating meth-
The engineering techniques are versatile. The ods [189]. Joining is usually carried out above
following working methods are of special impor- room temperature by soldering, brazing, or
tance: welding. Soldering may be used for all sorts of
hot working cold working copper, owing to the low temperature. However,
hot rolling cold rolling
extrusion cold drawing
welding and brazing are feasible only with de-
drop forging cupping oxidized or oxygen-free copper.
When tough-pitch copper is heated in an at-
Foils only ca. 0.002 mm thick are manufactured mosphere containing hydrogen, the steam gener-
by rolling, and wires to 0.004 mm diameter by ated (see page 7) collects within the grain bound-
aries at high pressure and can destroy the grain
56 Copper
structure by forming cracks. This phenomenon
is known as “hydrogen embrittlement.”
Mechanical joining and metal bonding are
also possible ways of joining copper with other
materials.
Surface treatment of copper is a group of
operations for surface protection or surface re-
finement. These include mechanical, electri-
cal, or electrochemical handling, e.g., polish-
ing, matte finishing, pickling by dilute sulfu-
ric or nitric acid, metal coating or electroplating
(with nickel, nickel and chromium, tin, silver,
gold, or platinum metals), lacquering or coat-
ing with synthetic plastics (mainly for electrical
insulation), enameling of objects (applied art),
and chemical or electrochemical coloring (dec-
oration). Coloration is effected by chemicals,
mostly specially formulated metal salt solutions
which form thin layers of insoluble green, red,
brown, or black compounds.
7.3. Uses
Copper is a useful material with a wide range of
applications because of its combination of prop-
erties. Because of its excellent electrical con-
ductivity, it is the dominant conductor material.
Copper is used primarily as round wire or rods,
bare or insulated, for current generation, trans-
mission, and conduction; various sorts of cables
are produced for special applications. Substan-
tial quantities of copper are made into genera-
tors, motors, transformers, and other electrical
appliances. About 40 % of the world consump-
tion of copper is for electrical purposes. As a
result of its high thermal conductivity, copper is
well-suited for vessels and pipes, especially for
heating, cooling, and heat exchange.
While high-conductivity copper is required
for electrotechnical and electronic uses, special
copper qualities are chosen for other uses. About
30 % of world copper production is used for al-
loying. Copper alloys are usually cold-worked;
only ca. 10 % of them are cast.
Copper is frequently used in the chemical and
food industries because of its high resistance to
corrosion. There is substantial use of copper in
mechanical engineering, by fabricators of pre-
cision implements, in vehicle construction, and
in ship building. There is increasing interest in
copper building construction as a material for
installation, wall lining, and roofing. Hydraulic
engineers use copper sheets for tightening on
dams, sluices (floodgates), and bridges.
Other areas of application are in the fabrica-
tion of household articles, art objects, coins and
medals, and in military hardware as ammunition.
There is a smaller demand for other purposes,
such as electrodeposition; powder-metallurgical
copper, special materials for brakes and self-
lubricating bearings, small precision parts, fil-
ters, graphite brushes; and alloying additives for
aluminum, iron, and steel. Use in copper com-
pounds, chiefly copper sulfate and copper ox-
ides, consumes only 1 – 2 % of the primary world
production.
Table 22 lists the distribution of copper con-
sumption among various industries.
Table 22. Industrial use of copper (including alloys) in the Western
world in 1995, percentage by country [190]
Branch United Europe Asia
States
Electrical and electronic industry 25 37.5 50
Industrial machinery and 11 9 9
equipment
Building construction 43 39.5 15
Transportation 9 6.5 11
Consumer and general products 12 7.5 15
Substitution and Miniaturization. Several
materials compete with copper and may sub-
stitute for it, depending on the relative costs.
Copper is partly replaced by aluminum in au-
tomotive radiators and in transmission cables,
high-voltage long-distance lines, and household
wiring. Copper wires and cables for telecom-
munications are being displaced by microwave
technology and fiber optics. Copper is being
replaced by plastics for water pipes in both res-
idential and commercial construction. In the
area of corrosion-resistant materials, in addi-
tion to plastics there are also stainless steel and
titanium.
The movement toward making smaller and
smaller parts has been one of the most pervasive
and continuing pressures on the copper market.
A dramatic drop in the use of copper has oc-
curred in the widespread acceptance of printed
circuits. The use of wire has plummeted. The
number and size of the connectors have dropped.
On the other hand, miniaturization has steadily

decreased the cost of the final products, thus in-
creasing the number of units sold.
At the same time, however, this drive towards
miniaturization, whether in the thickness of an
automotive radiator or in the size of an electronic
component, is a challenge to the copper industry
to produce purer copper and more useful alloys
and to the copper fabricating industry to produce
the new miniaturized products.
In several applications copper is resisting
substitution by using new technologies. For ex-
ample in telecommunications, copper continues
to be the preferred signal carrier for the last mile.
The new xDSL (Digital Subscriber Line) tech-
nology allows the existing copper infrastructure
of ordinary telephone wires to also carry high-
speed data. The installation of optical fiber in
communication trunk lines has led to a revolu-
tion in the telecom industry. Copper application
was partly displaced, but overall this increased
the demand for copper. Another development is
the use of copper circuitry in silicon chip tech-
nology, which makes the microprocessors faster
and lowers energy consumption. Another exam-
ple is the automobile radiator, which was for-
merly made of copper, which was then displaced
by aluminum. New technology was developed
for producing smaller and lighter copper brass
radiators with higher thermal conductivity than
aluminum radiators. A final example for innova-
tion in copper is the development of supercon-
ducting power cables made from high-tempera-
ture superconductor wire. This technology will
improve energy efficiency, and now projects in
Chicago and Tokyo have been started.
8. Economic Aspects
There are numerous tabular compilations of
statistics on copper resources, production, and
consumption [192–196]. Many books deal with
economic relations and commercial problems,
e.g., [197–200]. Compilations of companies in
the nonferrous metal industry [201] and the min-
ing industry [202] are published at irregular in-
tervals.
Production and Consumption. The copper
production of mines, smelters, and refineries and
the consumption by country and region are given
in Table 23. Over the decades, the annual per
Copper 57
capita consumption of primary copper in the
United States has grown [195]:
Late twenties 7.5 kg
Early thirties 2.5 kg
World War II 9.5 kg
Postwar period 7.5 kg
1970 13.3 kg
1979 14.6 kg
During the 1980s, there has been no increase in
consumption in America and Europe and only a
small increase worldwide. In the 1990s copper
production increased due to industrial growth.
Figure 36 shows the development of world
per capita consumption for 1950 to 1997.
Cost of Copper Production and Copper
Price. The cost of copper production is char-
acterized by high capital investment in mining
projects and in smelters and refineries. Mining
projects are financed by large consortiums and
banks. The capital investment for a green-fields
smelter is in the region of 2500 – 3000 $/t of
design copper production. Smelter enlargement
investment is approximately half that. There-
fore, increased smelter production is preferably
achieved by enlargement.
In the last 15 years copper leaching projects
have been established. This is due to lower cap-
ital investment than smelters (about half), and
also leaching operations built to increases the
copper yield of ores.
Operational costs are high due to energy con-
sumption, which is the most important factor.
For primary copper production the overall en-
ergy consumption per tonne of copper is about
45 GJ, about half of which is consumed in min-
ing and beneficiation and the rest in smelting
and electrorefining. For secondary copper, com-
ing for example from copper scrap smelting and
refining, the overall energy consumption is only
20 GJ/t.
Due to several smelter enlargements, leach-
ing operations, and also new energy-efficient
milling and smelting/refining processes, the
overall production cost of copper are falling.
The copper price is set primarily at the two
metal exchanges: the London Metal Exchange
(LME) and the New York Commodity Exchange
(COMEX). Like the copper production cost also
the copper prices have been in an overall declin-
ing trend since the World War II. The copper
58 Copper
Table 23. Production and consumption of copper in 1997 (in 103 t)

Mine Production Metal ∗∗ Production Metal ∗∗ Consumption

Argentina 30.2 15.6 51.7

Armenia 1.9
Australia 560.0 271.1 181.7
Austria 77.0 31.0
Belgium-Luxembourg 386.0 363.3
Botswana 20.7
Brazil 40.0 177.1 254.6
Bulgaria 75.5 34.9 42.0
Canada 658.0 560.3 224.6
Chile 3 392.0 2 116.6 79.9
China 495.5 1 179.4 1 258.0
Colombia 1.8 4.0
Congo 40.1 40.1
Cyprus 3.9 3.9
Czech Rep. 9.7
Egypt 4.4 4.3
France 35.1 558.0
Georgia 4.0
Germany 673.6 1 040.0
Greece 96.8
Hungary 13.3
India 38.0 65.9 180.0
Indonesia 548.4 54.2
Iran 117.3 106.3 56.4
Italy 85.7 520.6
Japan 0.9 1 278.7 1 440.7
Kazakhstan 316.2 301.1 13.7
Korea (North) 10.0 30.0 15.0
Korea (Rep.) 262.6 624.3
Macedonia 13.0
Malaysia 18.9 159.6
Mexico 393.1 297.0 239.7
Mongolia 130.0 3.0
Marocco 15.4
Myanmar 6.0
Namibia 20.3
Netherlands 40.4
Oman 23.6
Pakistan 11.0
Papua New Guinea 111.5
Peru 503.3 384.1 48.0
Philippines 48.6 146.6 45.5
Poland 414.7 440.6 233.0
Portugal 106.5 1.4
Romania 23.2 22.9 14.5
Russian Fed. 526.0 610.0 165.0
Saudi Arabia 1.0 145.0
Scandinavia ∗ 101.8 277.2 264.5
Singapore 10.3
Slovakia 23.0 28.0
South Africa 185.6 130.2 81.8
Spain 38.3 292.0 203.0
Switzerland 7.5
Taipei, China 587.8
Thailand 151.9
Turkey 65.0 113.7 194.4
United Kingdom 60.4 408.5
United States 1 940.0 2 452.4 2 790.0
Uzbekistan 74.4 115.0 10.0
Venezuela 18.0
Yugoslavia Fed. 73.6 106.6 36.0
Zambia 352.9 338.4 17.7
Zimbabwe 6.8 17.9 15.0
Others 1.8 16.0
TOTAL 11 526 13 564 13 084

∗ Scandinavia includes Finland, Norway, and Sweden. ∗∗ Refined copper.

 Copper 59

Figure 36. Per capita consumption of refined copper, 1950 – 1997

a) Relative per capita copper consumption; b) World population
Base index figures for 1950 are a copper consumption of 1.07 kg per capita and a world population of 2.5 × 109

price also increases and decreases in the same effects on health, vegetation, and property. In
economic cycles as industrial growth and reces- most cases, sulfuric acid is produced from the
sion. The development of copper prices since SO2 -containing off-gas (→ Sulfuric Acid and
1960 is shown in Figure 37. Sulfur Trioxide) [206].
Table 24. Comparison of SO2 concentrations in copper smelting
Product Information. Information on off-gas [203]
recent developments in copper are Process SO2 , vol %
available at http://www.copper.org and
http://www.kupfer.org. Statistical data are avail- Multiple-hearth roasting 5–8
Fluidized-bed roasting 8 – 15
able at http://www.icsg.org. Sinter roasting 1–2
Blast furnace smelting 2–5
Reverberatory furnace smelting 0.5 – 2.5
Electric furnace smelting 0.5 – 5
9. Environmental Protection Outokumpu flash smelting 10 – 30
INCO flash smelting 75 – 80
KIVCET process 80 – 85
The worldwide growth of industry and popula- Peirce – Smith converter 5 – 12
tion has caused a series of environmental prob- Hoboken converter 7 – 17
TBRC process 1 – 15
lems, particularly the following: (1) emission Mitsubishi process 15 – 20
control; (2) water protection; (3) solid-waste dis- Noranda process 10 – 20
posal.
Flue dust can be separated from off-gas
Emission Control. There are two important to a high degree in modern gas-cleaning sys-
tasks in the treatment of off-gas from pyromet- tems such as electrostatic precipitators, bag-
allurgical processes in copper metallurgy: the houses, cyclones, and wet scrubbers. This metal-
removal of sulfur dioxide and the containment containing dust is recycled.
of flue dust.
Because most copper comes from sulfide Water Protection. Harmful wastewater
ores, sulfur is the main problem in copper ex- does not usually result from pyrometallurgi-
traction. In pyrometallurgical operations, it ap- cal copper production but water for direct or
pears as sulfur dioxide (Table 24) [204], [205]. indirect cooling of furnaces, casting machines,
The mass ratio of sulfur to copper in sul- and cast copper products is required on a large
fidic concentrates is usually between 0.8 and scale. This cooling water is moderately warmed,
1.6. Consequently, a large quantity of sulfur but does not acquire chemical impurities. Closed
dioxide must be captured because of its harmful
60 Copper

Figure 37. Development of copper prices since 1960

a) Cu price (current); b) Cu price (constant 1996)

circulation is used as much as possible in mod- 3) Hydrometallurgical techniques yield various

ern plants. precipitates such as elemental sulfur or im-
Hydrometallurgical operations for the extrac- pure gypsum, which can easily be deposited.
tion of copper from ores or concentrates present
the risk of water pollution. These solutions, of
various compositions, must be posttreated if they
cannot be recycled. Such posttreatment consists 10. Toxicology
of neutralization or precipitation of specific ions,
chiefly anions bearing sulfur and the cations of Copper is a vital trace element for humans, most
heavy metals. Lime is an excellent precipitant. animals, and plants. The copper content of an
Thus, the sulfate ion in sulfuric acid solutions adult human ranges from 50 to 120 mg. The av-
formed during hydrometallurgical extraction is erage dietary intake of copper by adults ranges
precipitated as gypsum [208]. from 0.9 to 2.2 mg/d. For higher organisms, the
compact metal is completely harmless. However
Solid-Waste Disposal. The following Protista, especially bacteria, die in contact with
means are used for handling solid residues: metallic surfaces of copper and many of its al-
1) Recycling loys (oligodynamic effect) [209], [210].
2) Exploitation as raw material for the prepara- Continued exposure to the metal dust or
tion of useful products fumes can irritate mucous membranes. The fol-
3) Dumping in deposits lowing exposure limits have been established:
One example of each method follows:
1) Flue dust from pyrometallurgical operations, Form Federal Republic of United States
e.g., from the Outokumpu flash smelting pro- Germany
cess, are added to the feed and recycled into
Metal MAK TLV/STEL
suitable furnaces (Section 5.5.1) and occa- dust 1 mg/m3 2 mg/m3
sionally into blast furnaces after agglom- Metal MAK TLV/TWA
eration (Section 5.4.1). Zinc-containing flue fumes 0.1 mg/m3 0.2 mg/m3

dusts can be processed into zinc and zinc

compounds.
2) Discarded slags with low copper content
from some copper smelting processes can be
sold after suitable treatment (Section 5.3.3).

11. References
General References
1. V. Tafel: Lehrbuch der Metallhüttenkunde, 2nd
ed., vol. 1, Hirzel, Leipzig 1951.
2. A. Butts: Copper – The Science and
Technology of the Metal, Its Alloys and
Compounds, Reinhold Publ. Co., New York
1954.
3. N. N. Muratsch: Handbuch des
Metallhüttenmannes, vol. 1, VEB-Verlag
Technik, Berlin 1954.
4. Gmelin, system no. 60, “Kupfer,” Part A
(1955).
5. H. Grothe (ed.): Lueger-Lexikon der Technik,
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University of Concepción, Chile, 1967.
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9. Winnacker-Küchler, 4th ed., vol. 4, p. 350.
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12. J. C. Yannopoulos, J. C. Agarwal (eds.):
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Refining,”Extractive Metallurgy of Copper,
vol. 1, The Metallurgical Society of AIME,
New York, N.Y., 1976; (AIME Annual
Meeting, Las Vegas 1976).
13. A. K. Biswas, W. G. Davenport: Extractive
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15. C. B. Gill: Nonferrous Extractive Metallurgy,
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Berlin-New York 1983.
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21. L. Aitchison: A History of Metals, vols. 1 and
2, Mac Donald & Evans Ltd., London 1960.
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und Hüttenwesen (1556), 5th ed., VDI-Verlag,
Düsseldorf 1978.
24. L. Suhling: Der Seigerhüttenprozeß,
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Deutscher Ingenieure (eds):
Werkstoff-Handbuch Nichteisenmetalle, 2nd
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28. K. Dies: Kupfer und Kupferlegierungen in der
Technik, Springer Verlag, Berlin 1961.
29. D’Ans-Lax: Taschenbuch für Chemiker und
Physiker, 3rd ed., vol. 1, Springer Verlag,
Berlin 1967.
30. Copper Development Assoc.: CDA Technical
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Electrochemistry, 6th ed., vols. 1 and 2,
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Inorganic Compounds, Int. Copper Res.
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hundert Jahre, Ges. Deutscher Metallhütten-
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37. E. Fromm, E. Gebhardt (eds.): Gase und
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Berlin 1976.
38. Bundesanstalt für Bodenforschung, Hannover,
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of Sulfide Concentrates, Stanford University,
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51. R. O. Thomas, D. W. Hopkins in [11], pp. 1 – 5.
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499 – 511.
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54. S. D. Michaelson et al., J. Met. 18 (1966)
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55. H. Schlegel, A. Schüller, Freiberg.
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