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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-


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

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


10.1002/14356007.a07 471
2 Copper

Etymology. According to mythology, the ginning ca. 2800 b.c. At first, copper ores
goddess Venus (or Aphrodite) was born on were smelted with tin ores; later, bronze was
the Mediterranean island of Cyprus, formerly produced from metallic copper and tin. Brass
Kypros (Greek), where copper was exploited (copper – zinc alloy) was known ca. 1000 b.c.
millennia before Christ. Therefore, in early and became widely used in the era of the Ro-
times the Romans named it cyprium, later called man Empire.
cuprum. This name is the origin of copper and of
the corresponding words in most Romance and In Roman times, most copper ore was mined
Germanic languages, e.g., cobre (Spanish and in Spain (Rio Tinto) and Cyprus. With the fall of
Portuguese), cuivre (French), Kupfer (German), the Roman Empire, mining in Europe came to a
koper (Dutch), and koppar (Swedish). virtual halt. In Germany (Saxony), mining activ-
ities were not resumed until 920 a.d. During the
History [21–24]. The first metals found by Middle Ages, mining and winning of metals ex-
Neolithic man were gold and copper, later sil- panded from Germany over the rest of Europe.
ver and meteoric iron. The earliest findings of In the middle of the 16th century, the current
copper are presumed to be nearly nine millen- knowledge of metals was compiled in a detailed
nia old and came from the region near Konya in publication [23] by Georgius Agricola, De
southern Anatolia (Turkey). Until recently the Re Metallica (1556).
six-millennia-old copper implements from Iran Independent of the Old World, the Indians of
(Tepe Sialk) were presumed to be the oldest. In North America had formed utensils by working
the Old World, copper has been worked and used native copper long before the time of Christ, al-
since approximately though the skills of smelting and casting were
unknown to them. On the other hand, the skill of
7000 b.c. Anatolia copper casting was known in Peru ca. 500 a.d.,
4000 b.c. Egypt, Mesopotamia, Palestine, Iran,
and Turkestan and in the 15th century the Incas knew how to
3000 b.c. Aegean, India win the metal from sulfide ores.
2600 b.c. Cyprus
2500 b.c. Iberia, Transcaucasia, and China
Around 1500, Germany was the world leader
2200 b.c. Central Europe in copper production, and the Fugger family
2000 b.c. British Isles dominated world copper trade. By 1800, Eng-
1500 b.c. Scandinavia
land had gained first place, processing ores from
her own sources and foreign pits into metal. Near
Empirical experience over millennia has led 1850, Chile became the most important producer
to an astonishing knowledge of copper metallur- of copper ores, and toward the end of the last
gical operations: century, the United States had taken the world
1) Native copper was hardened by hammering lead in mining copper ores and in production of
(cold working) and softened by moderate refined copper.
heating (annealing). Technical development in the copper indus-
2) Heating to higher temperatures (charcoal and try has made enormous progress in the last 120
bellows) produced molten copper and made years. The blast furnace, based on the oldest
possible the founding into forms of stone, principle of copper production, was continually
clay, and later metal. developed into more efficient units. Neverthe-
3) Similar treatment of the conspicuously col- less, after World War I, it was increasingly re-
ored oxidized copper ores formed copper placed by the reverberatory furnace, first con-
metal. structed in the United States. Since the end of
4) The same treatment of sulfide copper ores World War II, this furnace has been superseded
(chalcopyrite), however, did not result in cop- slowly by the flash smelting furnace invented
per metal, but in copper matte (a sulfidic in- in Finland. Recently, several even more mod-
termediate). Not before 2000 b.c. did people ern methods, especially from Canada and Japan,
succeed in converting the matte into copper have begun to compete with the older processes.
by repeated roasting and smelting. An important development in producing
5) In early times, bronze (copper – tin alloy) was crude metal was the application of the Besse-
won from complex ores, the Bronze Age be- 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- The distorted octahedral coordination of six wa-
dizes in the course of years to a mixture of green ter molecules around the Cu2+ ion (d 9 ) gives
basic salts, the patina, which consists chiefly an additional stabilization energy (ligand-field
of the basic sulfate, with some basic carbonate. effect). In aqueous solutions, Cu+ is only ex-
(In a marine atmosphere, there is also some ba- istent in form of very stable complexes like
sic chloride.) Such covering layers protect the [Cu(CN)2 ]− or in the presence of an excess of
metal. copper metal. Also, insoluble Cu+ compounds
such as cuprous oxide do not disproportionate
Behavior versus Diverse Substances. in water.
While many substances scarcely react with By virtue of its large ionic radius and low
copper under dry conditions, the rate of at- electrical charge, the Cu+ ion is a soft acid.
tack increases considerably in the presence of Therefore, the chemistry of copper in the oxida-
moisture. Copper has a high affinity for free tion state + 1 is predominated by reactions with
halogens, molten sulfur or hydrogen sulfide. soft bases like iodine (CuI), sulfur (CuSCN),
Standard electron potentials of copper are as or unsaturated nitrogen ligands. In contrast,
follows [31], [32]: the chemistry of Cu2+ , which is smaller and
Potentials in standard (acid) solution: more highly charged, is dominated by hard lig-
ands like oxygen ([Cu(H2 O)6 ]2+ ) or nitrogen
Cu+ + e− −→ Cu E 0 = 0.521 V ([Cu(NH3 )4 ]2+ ).
Copper is very stable in fresh water and
Cu2+ + 2 e− −→ Cu E 0 = 0.153 V also in sea water or alkali metal hydroxide so-
lutions. Wastewater containing organic sulfur
Potentials with complexing ligands: compounds can be corrosive to copper.
[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 Figure 1. Pourbaix diagram for copper in highly dilute aque-
with oxygen or hydrogen peroxide attacks cop- ous solution at normal temperature [35]
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. Corrosion [33], [34]. M. J. N. Pourbaix
Spontaneous disproportion into Cu2+ and Cu has developed potential – pH equilibrium dia-
takes place. grams for metals in dilute aqueous solutions
[35]. Such graphs give a rough indication of the
2 Cu+ −→ Cu2+ + Cu E 0 = 0.37 V 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-
K = [Cu2+ ]/[Cu+ ] = 106 ter:
Copper 7

1) Corrosion, in which the metal is attacked It is thus about half as abundant as chromium,
2) Immunity, in which reaction is thermody- about twice as abundant as cobalt, and 26th in
namically impossible order of abundance of the elements in the acces-
3) Passivity, in which there is no reaction be- sible sphere of the earth. Table 5 shows average
cause of kinetic phenomena copper contents in natural materials.
Table 5. Typical copper contents of natural materials
Gases and Copper [36], [37]. An exact
knowledge of the behavior of solid and liquid Mineral Content, ppm
copper toward gases is important for production Basalt 85
and use of the metal. With the exception of hy- Diorite 30
Granite 10
drogen, [1333-74-0], the solubility of gases in Sandstone 1
molten copper follows Henry’s law: the solubil- Copper ores (poor) 5 000
ity is proportional to the partial pressure. Copper ores (rich) 50 000
Native copper 950 000
Oxygen [7782-44-7] dissolves in molten cop- Seawater 0.003
per as copper(I) oxide up to a concentration of Deep-sea clays 200
Manganese nodules 10 000
12.6 wt % Cu2 O (corresponding to 1.4 wt % O) Marine ore sludges 10 000
(also see Fig. 32). Copper(I) oxide in solid cop- Earth’s crust (average) 50
per forms a separate solid phase. Meteorites (average) 180
Sulfur dioxide [7446-09-5] dissolves in
molten copper and reacts:
6 Cu + SO2  Cu2 S + 2 Cu2 O
4.1. Copper Minerals
Hydrogen is considerably soluble in liquid cop-
per, and after solidification some remains dis- More than 200 minerals contain copper in defin-
solved in the solid metal, although copper does able amounts, but only about 20 are of impor-
not form a hydride. The solubility follows Siev- tance as copper ores (Table 6) or as semiprecious
ert’s law, being proportional to the square root stones (turquoise and malachite). Copper is a
of the partial pressure because the H2 molecules typical chalcophilic element; therefore, its prin-
dissociate into H atoms on dissolution. Hydro- cipal minerals are sulfides, mostly chalcopyrite,
gen has high diffusibility because of its ex- bornite, and chalcocite, often accompanied by
tremely small atomic volume. pyrite, galena, or sphalerite.
Hydrogen dissolved in oxygen-bearing cop- Secondary minerals are formed in sulfide ore
per reacts with copper(I) oxide at high tempera- bodies near the earth’s surface in two stages.
tures to form steam: In the oxidation zone, oxygen-containing wa-
−→ ter forms copper oxides, basic salts (basic car-
Cu2 O + 2 H ←− 2 Cu + H2 O(g)
bonates and basic sulfates), and silicates. In the
Steam is not soluble in copper; therefore, it ei- deeper cementation zone, copper-bearing solu-
ther escapes or forms micropores. tions from these salts are transformed into sec-
Nitrogen, carbon monoxide, and carbon diox- ondary copper sulfides (chalcocite and covel-
ide are practically insoluble in liquid or solid lite) and even native copper of often high purity,
copper. Hydrocarbons generally do not react e.g., in the Michigan copper district (Keweenaw
with copper. An exception is acetylene, which Peninsula).
reacts at room temperature to form the highly Other metallic elements frequently found in
explosive copper acetylides Cu2 C2 and CuC2 ; copper ores are iron, lead, zinc, antimony, and ar-
therefore, acetylene gas cylinders must not be senic; less common are selenium, tellurium, bis-
equipped with copper fittings. muth, silver, and gold. Substantial enrichments
sometimes occur in complex ores. For example,
ores from Sudbury, Ontario, in Canada contain
4. Occurrence nickel and copper in nearly the same concentra-
tions, as well as considerable amounts of plat-
In the upper part of the earth’s crust (16 km inum metals. The copper ores from Zaire and
deep), the average copper content is ca. 50 ppm.
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- 3) Hydrothermal ore deposits result by further
phyry copper ores in America contain significant cooling of the hot, dilute metal-bearing solu-
amounts of molybdenum and are the most im- tions from ca. 350 ◦ C downward, i.e., below
portant single source of rhenium. The extraction the critical temperature of water. Such de-
of precious metals and other rare elements can posits contain copper primarily as chalcopy-
be decisive for the profitability of copper mines, rite and satisfy ca. 50 % of the demand in
smelters, and refineries. the Western world. There are many exam-
ples of different types of hydrothermal de-
posits. Examples: Butte, Montana (gangue
4.2. Origin of Copper Ores deposit); Tsumeb, Namibia (metasomatic
deposit); Bingham Canyon, Utah; Chuquica-
Ore deposits are classified according to their mata, Chile; Toquepala, Peru; Bougainville,
mode of formation, but the origin of copper ores Solomon Islands (impregnation deposits).
is geologically difficult to unravel, and some Impregnation deposits are also called dis-
of the proposed origins are controversial. The seminated copper ores or porphyry copper
classification distinguishes two main groups, the ores (or simply porphyries) because of their
magmatic series and the sedimentary series. fine particle size.
Magmatic ore formation involves magma 4) Exhalative sedimentary ore deposits origi-
crystallization and comprises the following nate from submarine volcanic exhalations
groups: and thermal springs that enter into seawa-
ter, and constitute a transitional type to sedi-
1) Liquid magmatic ore deposits originate by mentary deposits. These ores are third in eco-
segregation of the molten mass so that the nomic importance in the Western world. The
heavier sulfides (corresponding to matte) actual formation of such sulfidic precipita-
separate from the silicates (corresponding tions can be observed, for example, the ma-
to slag) and form intrusive ore bodies. Ex- rine ore slimes in the Red Sea. Examples:
amples: Sudbury, Ontario; Norilsk, western Mount Isa, Queensland; Rio Tinto, Spain;
Siberia. Rammelsberg (Harz), Federal Republic of
2) Pegmatitic – pneumatolytic ore deposits de- Germany.
velop during the cooling of magma to ca.
The origin of sedimentary ore occurs in the
374 ◦ C, the critical temperature of water. Ex-
exogenous cycle of rocks and may be subdivided
amples: Bisbee, Arizona; Cananea, Mexico.
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 World primary copper reserves were estimated
weathering with uneven mineralization. Ex- in 1991 at 552 × 106 t (Table 7) [41]. Reserves
amples: Dsheskasgan, Kazakhstan; Exótica, are identified resources and do not include
Chile. undiscovered resources. With time the avail-
2) Partly metamorphized sedimentary ores in able reserves have increased because of techni-
shales, marls, and dolomites form large cal progress in processing ores with low copper
strata-bound ore deposits, especially in the content and the discovery of new ore deposits
African copper belt, and represent the second [38], [39]. About 321 × 106 t were classified as
most important source of copper to the West- minable copper ores under the technical and eco-
ern world, as well as supplying nearly 75 % of nomical conditions at that time.
its cobalt. Examples: Zaire (oxidation zone, It is believed that a large potential of as-yet
oxidized ores 6 % Cu); Zambia (cementa- untouched deposits exist. Therefore, the poten-
tion zone, secondary sulfide ores 4 % Cu). tially usable copper resources are estimated to
3) Marine precipitates have formed sedimen- be about three times as large as the reserve base.
tary ore deposits similar to the present phe- In addition to ores on land, there is an estimated
nomenon of sulfide precipitation by sulfur amount of copper in deep-sea nodules of about
bacteria in the depths of the Black Sea. Ex- 0.7 × 109 t.
amples: Silesia (copper marl), Poland. Table 7. Copper ore reserves in 1991 [41]
4) Deep-sea concretions lie in abundance on the
bottom of the oceans, especially the Pacific Country Ore reserves, Percentage of
Ocean. These so-called manganese nodules 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- Ocean mining involves obtaining metallifer-
tial mine. The used geological, geochemical, or ous raw materials from the deep oceanic zones.
geophysical methods are complicated and ex- Two groups of substances are of interest: deep-
pensive. But often legal and political factors are sea nodules [43] and marine ore slimes [44]. The
more decisive for a new mine project than tech- nodules (manganese nodules; see → Manganese
nological or financial aspects. The methods used and Manganese Alloys, Chap. 9.) contain, in
for exhausting the copper ore are depending to addition to iron oxides, ca. 25 % Mn, 1 % Ni,
a great extent to the type of deposit. Important 0.35 % Co and 0.5 % (max. 1.4 %) Cu. Spe-
parameters are metal content of the ore and ge- cially equipped ships have collected and lifted
ometry and depth of the ore body. These pa- these nodules from depths of 3000 – 5000 m;
rameters determine the working method. Under- specific metallurgical and chemical methods for
ground and open-cast mining are the two basic processing the nodules have been developed in
techniques. As a generalization mining can be pilot plants. Because of the extremely high ex-
divided into the stages drilling, blasting, load- penses, large-scale operations of this type have
ing, and haulage of the ore. not yet been undertaken. Marine ore slimes from
Technological developments like the LHD the Red Sea (2200-m depth) average ca. 4 % Zn,
technique (load, haul, dump) and the use of 1 % Cu, and a little silver. Although methods for
concrete for stowing have made mining more processing these slimes have been investigated,
cost efficient. But underground mining is still this resource is not now economically important.
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- 5. Production
tain other valuable metals in addition to copper
(e.g., precious metals, nickel, cobalt) are mined Over the years copper production methods have
underground, while ores with 0.5 % Cu, which been subjected to a continual selection and im-
represents a 100-fold enrichment of the average provement process because of the need for (1) in-
copper content in the earth’s crust, are mined creased productivity through rationalization, (2)
by open-cast methods. The porphyry copper de- lower energy consumption, (3) increased envi-
posits which are located near the surface can ronmental protection, (4) increased reliability of
only be exploited by open-cast technique. They operation, and (5) improved safety in operation.
have become more important during the last During this development a number of tendencies
decades. The first open pit was started at Bing- have become apparent:
ham Canyon early this century. Today the ter-
raced copper open pits are the largest ore mines 1) Decrease in the number of process steps
in the world. They often cover more than one 2) Preference for continuous processes over
square kilometer and have working depths of batch processes
several hundred meters. 100 000 t of crude ore 3) Autogenous operation
are extracted per day. Today more than 50 % of 4) Use of oxygen or oxygen-enriched air
the primary copper comes from open pits. Other 5) Tendency toward electrometallurgical meth-
less common methods for copper extraction are ods
in situ leaching or ocean mining. 6) Increased energy concentration per unit of
In situ leaching is a hydrometallurgical pro- volume and time
cess in which copper is extracted by chemical 7) Electronic automation, measurement, and
dissolution in sulfuric acid. This method is suit- control
able for low-grade copper ore bodies for which 8) Recovery of sulfur for sale or disposal
customary mining operations would be uneco- 9) Recovery of valuable byproducts
nomical, as well as for the leaching of remenant
ores from abandoned mines. In some cases, the The selection of a particular production
ore body must be broken before leaching by method depends essentially on the type of avail-
blasting with explosives to increase the surface able raw materials, which is usually ore or con-
area for chemical reaction. centrate and on the conditions at the plant loca-
tion.
Copper 11

About 80 % of primary copper production grinding in semi-autogenous rod or autogenous


comes from low-grade or poor sulfide ores. Af- ball mills takes place. Size classification takes is
ter enrichment steps, the copper concentrates performed in cyclones. In the next step of bene-
are usually treated by pyrometallurgical meth- ficiation, valuable minerals and gangue are sep-
ods. Generally, copper extraction follows the se- arated by froth flotation of the ore pulp, which
quence: exploits the different surface properties of the
1) Beneficiation by froth flotation of ore to give sulfidic copper ore and the gangue [46]. The hy-
copper concentrate drophobic sulfide particles become attached to
2) Optional partial roasting to obtain oxidized the air bubbles, which are stirred into the pulp,
material or calcines rise with them to the surface of the pulp, and are
3) Two-stage pyrometallurgical extraction skimmed off as a froth of fine concentrate. The
hydrophilic gangue minerals remain in the pulp.
a) smelting concentrates to matte
Organic reagents with sulfur-containing groups
b) converting matte by oxidation to crude
at their polar end, such as xanthates, are used as
(converter or blister) copper
collectors in the flotation process. Additionally,
4) Refining the crude copper, usually in two modifiers like hydroxyl ions (pH adjustment)
steps are used to select different sulfide minerals, for
a) pyrometallurgically to fire-refined copper example, chalcopyrite and pyrite. Alcohols are
b) electrolytically to high-purity electrolytic used to stabilize the froth.
copper To obtain concentrates with highest possible
Figure 2 [13] illustrates the principal pro- purity and recovery rate, the flotation process
cesses for extracting copper from sulfide ore. usually consists of several stages which are con-
About 15 %, with an increasing trend, of the trolled by expert systems. Various sensors for
primary copper originates from low-grade oxi- particle size, pH, density, and other properties
dized (oxide) or mixed (oxidized and sulfidic) are installed. Figure 4 gives an overview of a
ores. Such materials are generally treated by hy- typical beneficiation process at a concentrator.
drometallurgical methods. In the first flotation stage, as much copper as
The very few high-grade or rich copper ores possible is recovered in a rougher concentrate
still available can be processed by traditional so that as little as possible goes to the tailings.
smelting in a shaft furnace. This process is also To increase the copper recovery rate, often these
used for recovering copper from secondary ma- tailings are leached with sulfuric acid. After re-
terials, such as intermediate products, scrap, and grinding, the rough concentrate is cleaned in sev-
wastes. eral flotation steps. After sedimentation in thick-
Figure 3 [13] illustrates the most important eners and filtration in automatic filter presses or
operations in copper extraction from various ox- vacuum filters (ceramic disk) the typical cop-
idic ores. per concentrate contains 25 – 35 % Cu and about
8 % moisture. The moisture content of the con-
centrate is a compromise between transporting
5.1. Beneficiation water (cost) and avoiding dust generation dur-
ing transport. Dewatered concentrates may heat
Sulfidic copper ores are too dilute for direct spontaneously or even catch fire; therefore, ap-
smelting. Smelting these materials would re- propriate precautions must be taken [47].
quire too much energy and very large furnace Copper concentrators typically treat up to
capacities. The copper ore coming from the mine 100 000 t of ore per day. They are located directly
(0.5 – 1 % Cu) must be concentrated by benefi- at the mines to achieve low transport costs. The
ciation. The valuable minerals like chalcopyrite copper recovery efficiency is over 90 %. About
are intergrown with gangue. Therefore, in the 95 % of the ore input goes into the tailings, which
first step the lumpy ore is crushed and milled are stored in large dams near the mine and are
into fine particles (< 100 µm) to liberate the in- used for water recycling to the flotation stages.
dividual mineral phases. Separation of special copper ores such as
Typical equipment for crushing to about those containing molybdenite or with high zinc
20 cm are gyratory and cone crushers. Then wet
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- Bor Smelter [212]. Since ca. 1975 combined
tion methods. Flotation of non-sulfide copper roasting and matte smelting processes such as
minerals is rare because these ores are mostly flash smelting have been favored because of their
subjected to hydrometallurgical copper recov- lower energy consumption and process gas han-
ery, for example, heap leaching. In Zambia and dling advantages.
Zaire, however, siliceous copper oxide ores are The roasting process has several effects:
floated with fatty acid collectors, and dolomitic 1) Drying the concentrates
copper oxide ores are sulfidized with sodium hy- 2) Oxidizing a part of the iron present
drogensulfide and then floated [48]. 3) Controlling the sulfur content
4) Partially removing volatile impurities, espe-
cially arsenic
5.2. Roasting 5) Preheating the calcined feed with added
fluxes, chiefly silica and limestone
Roasting can be used to prepare sulfide concen-
trates for subsequent pyrometallurgical or hy- Chemical Reactions. When the moist con-
drometallurgical process. Partial roasting under centrates, which contain many impurity ele-
oxidizing conditions may be carried out prior ments, are heated, a multitude of chemical reac-
to smelting in reverberatory or electric furnaces. tions occur. Because analysis of the many ther-
Complete oxidizing or sulfatizing roasting may modynamic equilibria is not practical, a few fun-
be performed before leaching operations, espe- damental systems are usually chosen. The most
cially if other valuable metals such as cobalt are important is the ternary copper – oxygen – sulfur
present in the concentrate. Reducing roasting system (Fig. 5). The next most important system
may be carried out if copper concentrates with is the ternary iron – oxygen – sulfur system be-
very high contents of impurities such as As are cause most sulfidic copper ores contain signifi-
to be smelted. cant amounts of iron.
However, roasting processes are today not Initially, sulfides such as pyrite and chalcopy-
very important for the copper extraction pro- rite decompose and generate sulfur vapor, which
cess. Only a few plants are still operating, for reacts with oxygen to form sulfur dioxide:
example Boliden’s Rönnskär Smelter [211] and 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 1) Partial (oxidizing) roasting is the conven-
metal oxides, sulfur trioxide, and metal sulfates, tional way of extracting copper from sul-
are exothermic. fide concentrates. At 700 – 750 ◦ C, the de-
gree of roasting is determined by controlling
MS + 1.5 O2  MO + SO2 the access of air. A predetermined amount of
sulfur (30 – 50 % is removed, and only part
SO2 + 0.5 O2  SO3 of the iron sulfide is oxidized. The copper
sulfide is relatively unchanged. These con-
MO + SO3  MSO4 ditions are important for the formation of a
suitable matte.
In addition, there are secondary reactions, such 2) Total, or dead, roasting is occasionally used
as the formation of basic sulfates, ferrites (espe- for complete oxidation of all sulfides for a
cially magnetite), and silicates, the last provid- subsequent reduction process or for special
ing most of the slag in the subsequent smelting: hydrometallurgical operations.
3) Sulfatizing roasting is carried out at
MO + MSO4 −→ MO · MSO4 550 – 650 ◦ C to form sulfates. This method
yields calcines well-suited for hydrometal-
MO + Fe2 O3 −→ MFe2 O4 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 The ternary Cu – Fe – S system is discussed in
smelting is that between the oxides and sulfides detail in the literature [55–57]. Figure 6 shows
of copper and iron: the composition of the pyrometallurgically im-
portant copper mattes and the liquid-phase im-
Cu2 O + FeS  Cu2 S + FeO miscibility gap between matte and the metallic
phase. In the liquid state, copper matte is essen-
Iron(II) oxide [1345-25-1] reacts with added sil- tially a homogeneous mixture of copper(I) and
ica flux to form fayalite [13918-37-1], a ferrous iron(II) sulfides: the pseudobinary Cu2 S – FeS
silicate that is the main component of slag: system.
Arsenides and antimonides are soluble in
2 FeO + SiO2 −→ Fe2 SiO4
molten matte, but their solubility decreases with
Liquid iron sulfide [1317-37-9] reduces higher an increasing percentage of copper in the matte.
iron oxides to iron(II) oxide: Accordingly, when the arsenic concentration is
high, a special phase, the so-called speiss, can
3 Fe2 O3 + FeS −→ 7 FeO + SO2 (g) separate. It is produced under reducing condi-
tions in the blast or electric furnace, and its
3 Fe3 O4 + FeS −→ 10 FeO + SO2 (g) decomposition is complicated (→ Arsenic and
Arsenic Compounds, → Antimony and Anti-
The second reaction serves to remove magnetite mony Compounds).
[1309-38-2], which complicates furnace opera- Compositions of several copper mat-
tions because of its high melting point (1590 ◦ C) tes are shown in the partial diagram
[54]. Cu2 S – FeS – (Fe3 O4 + FeO) (Fig. 7), which is a
The pyrometallurgical production of copper section of the quaternary Cu – Fe – O – S system.
from sulfide ore concentrates may be considered The density of solid copper mattes ranges bet-
as a rough separation of the three main elements ween 4.8 g/cm3 (FeS) and 5.8 g/cm3 (Cu2 S);
as crude copper, iron(II) silicate slag, and sulfur liquid mattes have the following densities:
dioxide. About 20 accompanying elements must 4.1 g/cm3 (30 wt % Cu, 40 wt % Fe, 30 wt % S),
be removed from the copper by subsequent refin- 4.6 g/cm3 (50 wt % Cu, 24 wt % Fe, 26 wt % S),
ing. Table 8 shows the distribution of important and 5.2 g/cm3 (80 wt % Cu, 20 wt % S).
impurities among matte, slag, and flue dust. Pre-
cious metals, such as silver, gold, platinum, and
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- Around 1700, reverberatory furnaces were con-
inated, reduction with hydrogen and chlorina- structed in which the ore was processed by roast-
tion, but without leading to commercialization. ing, the so-called English or Welsh copper smelt-
ing process, originally with ten process steps.
Reduction. A potential process involves the The large blast and reverberatory furnaces of
reduction of chalcopyrite [70]: the 1900s were derived from these principles.
Later, the electric furnace for matte smelting
2 CuFeS2 + 3 H2 + 3 CaO −→ Cu2 S + 2 Fe + 3 CaS + 3 H2 O was developed. Newer processes are the Isas-
melt/Ausmelt/Csiromelt (furnace with vertical
CuFeS2 + 2 H2 + 2 CaO −→ Cu + Fe + 2 CaS + 2 H2 O blowing lance), the Noranda and CMT/Teniente
reactors (developed from converters), the Rus-
sian Vanyukov, and the Chinese Bayia process.
The reduction by hydrogen is endothermic,
but the overall reaction with calcium oxide is
exothermic. A similar proposal [71] is based on 5.4.1. Blast Furnace Smelting
the reaction of a metal sulfide with steam in the
presence of calcium oxide: 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
Chlorination. The reactions of chalcopyrite currently used in only a few places, for example,
with chlorine are also of interest [72]: Glogow in Poland.
>500 ◦ C: Smaller types of blast furnace, however, are
used to process such copper-containing materi-
CuFeS2 + 2 Cl2 −→ CuCl2 + FeCl2 + 2 S als as intermediate products (e.g., cement cop-
per or copper(I) oxide precipitates), reverts (e.g.,
<500 ◦ C: converter slag, refining slag, or flue dusts), and
copper-alloy scrap.
CuFeS2 + 3.5 Cl2 −→ CuCl2 + FeCl3 + S2 Cl2 The construction of the furnace is basically
followed by electrolysis of the molten copper related to that of the iron blast furnace, but
(I) chloride. there are considerable differences in design, es-
The recently proposed thermoelectron chlo- pecially in size and shape: the copper blast fur-
rination process is another variation [73]: nace is lower and smaller, and its cross section
is rectangular. Developments adopted from the
CuFeS2 + 2 Cl2 −→ CuCl + FeCl3 + 2 S
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-
Electrolysis. Another approach, to avoid tions of mixture (copper-containing materials
converting, proposed the electrolysis of molten and accessory fluxes such as silica, limestone,
copper matte [74]. and dolomite) and coke (which serves as both
fuel and reducing agent). There are three zones
in the furnace:
5.4. Traditional Bath Smelting 1) In the heating zone (the uppermost), water
evaporates and less stable substances disso-
At the end of the Middle Ages, copper was pro- ciate.
duced by the German or Swedish smelting pro- 2) In the reduction zone, heterogeneous reac-
cess that involved roasting reduction with up tions between gases and the solid charge take
to seven process steps in small shaft furnaces. place.
Copper 21

3) In the smelting zone, liquid phases react. or a mixture of concentrate and calcine could
The usual mode of operation is reduc- be processed. The charge is passed into the fur-
ing smelting, which yields two main prod- nace near the burners through the roof or lateral
ucts. Sulfide ores are used to produce a openings. As fossil fuel, pulverized coal, heavy
matte (40 – 50 wt % Cu) and a disposal slag oil, or natural gas is used. Normally the burner
(ca. 0.5 wt % Cu). In contrast, oxide ores are is located in the front wall of the furnace. The
processed directly to impure black copper atmosphere is slightly oxidizing, and the maxi-
(95 wt % Cu) and to a copper-rich slag. The mum flame temperature is up to 1500 ◦ C. During
two ore types can be smelted together to pro- the 1980s oxygen – fuel burners have been set in
duce matte and a slag with low copper content. the roof to fire downwards directly on the top of
Another product is top gas, which contains flue the bath. This increases the smelting rate by up
dust. Ores that contain high concentrations of to 40 % and the energy efficiency to about 50 %
arsenic and antimony also form speiss, which is [76], [215]. Another invention was the sprinkler
difficult to decompose. burner for feeding concentrate, coal, and flux
In Poland (KGHM Polska Meidz S.A. from the top of the reverb [77].
Smelters in Glogow I and Legnica) the blast- The back half of the furnace is the settling
furnace technology is well adapted to Pol- zone. A matte grade of between 35 and 60 % Cu
ish copper concentrates, which contain about is produced, depending on whether concentrate
20 – 30 % Cu like normal chalcopyrites but also or calcine is fed. The slag has low copper con-
5 – 10 % of organic carbon and only 9 – 12 % S. tent (< 1 %). Normally, the converter slag is also
Also these concentrates have relatively high lead fed back to the reverb. Sometimes problems with
(up to 2.5 %) and arsenic (up to 0.3 %) content. solid magnetite accretions in the furnace occur.
The organic carbon compounds provide about The off-gas has a temperature of about
40 – 60 % of the process energy; the rest is added 1250 ◦ C. It is diluted by the combustion air and
by coke. The matte has about 58 – 63 % Cu and contains only about 1 – 2 % SO2 . This is too
3 – 6 % Pb. The slag contains less than 0.5 % low for efficient SO2 capture such as sulfuric
Cu. The off-gas from the blast furnaces (three acid production by the contact process. Improve-
in each plant) is mixed with the converter gases ments have been achieved by using higher oxy-
(Hoboken Converter). It contains 7 – 10 % SO2 gen enrichment of the burners, but the off-gas
and is sent to sulfuric acid production. The pro- is still too dilute, and therefore this furnace is
duction figures are 80 000 t/a converter copper unsuitable for many regions in the world be-
in Legnica, and 200 000 t/a in Glogow I Smelter cause of environmental problems. Another dis-
[214]. advantage is the very high energy consumption.
The reverb has the highest energy consumption
of all copper matte smelting processes. A good
5.4.2. Reverberatory Furnace Smelting present example for operating reverbs is the Ilo
Smelter in Peru (Table 11). There two reverbs
The reverberatory furnace dominated copper smelt about 2000 t/d of concentrate, producing a
matte smelting for much of the 1900s, because it matte containing 35 % copper for the subsequent
was an excellent process for smelting fine con- Peirce – Smith converters. In the latest smelter
centrate from flotation. It is a fossil fuel fired enlargement one reverb was replaced by an Te-
hearth furnace for smelting concentrate and pro- niente converter (CMT), and a sulfuric acid plant
ducing copper matte. The reverbs began to de- for partial SO2 recovery was built.
cline in the 1970s with the adoption of environ-
mentally and energetically superior processes
like flash smelting. Probably the last one was 5.4.3. Electric Furnace Smelting
erected in 1976 in Sar Chemesh, Iran. In 1980
about 100 reverbs were in operation, but in 1994 In regions where relatively cheap electrical
the number had decreased to about 25. As shown power was available, electric furnaces were
in Figure 10 it is a rectangular furnace up to built. The Scandinavian countries were the first
10 m wide and 35 m long with internal brick lin- to perform electric matte smelting: 1929 at Sulit-
ing. Throughputs of up to 1100 t/d concentrate 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 Peirce – Smith converter for increasing exist-
are no tuyeres and the bath is quiet enough for ing smelter capacity. The Teniente process has
matte and slag settling. The matte usually con- been widely adopted in Latin America. Like
tains 70 – 75 % Cu (white metal) and is sent to the Noranda reactor, it is a robust technology
a subsequent converter. This operation gives a but has still not demonstrated that it can meet
large heat evolution from Fe and S oxidation in the highest environmental standards. The fur-
the Noranda furnace. This avoids excessive re- naces are horizontal cylinders, 4 – 5 m in diam-
tention of impurities like Sb in the matte. The eter and 14 – 22 m long (Figure 13). Inside, the
slag contains about 3 – 7 % copper and goes to converter is brick-lined, and it has 30 – 50 tuy-
further treatment like electric furnace or solidifi- eres for blowing oxygen-enriched air (30 – 32 %
cation/comminution/flotation. The off-gas con- O2 ). Solid feed such as wet concentrate, flux,
tains about 15 – 20 % SO2 . It passes through the or recycled materials are blown continuously
large mouth at the top of the reactor into a hood through a high-pressure gun (Garr gun) on the
and is sent to cooling, cleaning, and sulfuric acid top of the molten bath. Dry concentrate is in-
production. In case of emergencies the furnace jected additionally through four or five tuyeres
can be rolled out so that the tuyeres have a secure in the bath. Molten matte (35 – 40 % Cu) coming
position above the molten bath. 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
Figure 12. Noranda furnace gas is cooled with water sprays, the flue dust is
The Noranda process is well suited for smelt- stripped and then the gas is sent to sulfuric acid
ing scrap and residues, ashes, precious metals production (or in some cases to the stack).
scrap, telephone scrap, and computer/electronic With its molten-matte requirement, the CMT
scrap. Due to the high temperature and smelting is dependent on the operation of a reverbera-
intensity, potentially harmful organics are oxi- tory furnace with all the associated environmen-
dized to CO2 and H2 O. The productivity can be tal problems (SO2 emission). To overcome this
increased by using higher oxygen enrichment. reliance, some possibilities have been tested,
Then less fossil fuel is needed and the amount all of which increase the energy in the vessel:
of off-gas decreases. increased oxygen enrichment of the blast, in-
creased injection of dry concentrate through the
tuyeres, and burning small amounts of fossil
5.4.6. CMT/Teniente Process fuel. Today there are CMTs which do not need
low-grade molten matte.
The Caletones Matte Treatment (CMT) or so
called Teniente process [220], [221] is similar to
the Noranda process. The important differences 5.4.7. Vanyukov Process
are that no coal is included in the charge and
molten low-grade copper matte is periodically The Vanyukov process was developed in the
added as fuel. Therefore, the Teniente furnace is 1970s in Norilsk, Russia. It is similar to the No-
mostly regarded as a converter. randa process, but the furnace is rectangular with
The process was developed at Teniente tuyeres on both sides, blowing highly enriched
Smelter by adding dry concentrate to a air ( 70 – 90 % O2 ) in the slag zone (Figure 14).
Copper 25

Figure 13. Teniente converter (CMT)

Moist copper concentrate is charged through 5.5. Autogenous Smelting


ports in the roof of the furnace. The process pro-
duces matte (ca. 50 % Cu), slag (1.5 – 2 % Cu) Autogenous smelting involves the use of com-
and off-gas (ca. 30 % SO2 ). The furnace oper- bustion heat generated by reactions of the feed
ates continuously, and the matte and slag leave in an oxidizing atmosphere in which the sulfide
the furnace continuously through two siphons. concentrate acts partly as a fuel. The formerly
The matte is sent to converting process, and the separate steps of roasting and smelting are com-
slag is cleaned in an electric furnace [222], [223]. bined into a roast – smelting process. The spatial
In contrast to the Noranda furnace the and temporal coupling of exothermic and en-
Vanyukov reactor is stationary. The tuyeres can dothermic reactions leads to an economical pro-
not be tilted out of the bath in emergency situ- cess, but the sensible heat of nitrogen in the air
ations. The advantage of the stationary system causes a deficit in the heat balance. In practice,
is the simple and very efficient SO2 capture. Six various measures must be taken:
Vanyukov furnaces are running in the CIS. With
a relatively small furnace (10 m long, 2 m wide, 1) Increasing the oxygen content of the com-
and 6 m high) about 1500 to 2000 t/d concentrate bustion air and even using pure oxygen
can be processed. 2) Preheating combustion air with waste heat or
All the submerged-tuyere processes like No- in a preheater
randa, CMT, and Vanyukov have relatively short 3) Combustion of natural gas, fuel oil, or pul-
campaign lifetimes (one year) because of high verized coal in supplementary burners
erosion in the tuyere zone. To achieve autogenous operation and prevent
agglomeration of the feed, the moisture in the
concentrate must be removed by drying before
5.4.8. Baiyin Process charging. The quantity of added fluxes is mini-
mized as far as practical to save energy.
At the Baiyin Copper Smelter in China, a process Because the residence time of the sulfide par-
similar to the Noranda furnace was developed ticles in the reaction chamber is only a few
in the 1980s [78]. Concentrate is added on the seconds, kinetic conditions predominate over
top of the molten bath, and air/oxygen is blown the thermodynamic equilibrium. The reactants
through submerged tuyeres into the melt. The form a heterogeneous system, with the feed sus-
Baiyin furnace has a wall inside to divide the re- pended in the gas flow, thus the term smelting in
action and the settling zone. In China there are suspension.
at least two furnaces in operation, but few data These processes have several advantages:
are available.
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 and four slag tapholes. The reaction shaft and
high concentration of SO2 and low quantity large areas of the settler and the gas off take are
of flue dust, if oxygen is used water-cooled to prevent overheating and weak-
However, a typical disadvantage is the high cop- ening of the furnace structure. The reaction shaft
per content of the slags, and the relatively high of many furnaces is cooled by cascading water
flue dust content in the off-gas, which can cause outside the steel shell. The other areas are usu-
problem in the waste-heat boiler. ally cooled by special copper cooling jackets,
which are built into the furnace walls [224].

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 Figure 15. Outokumpu flash smelting furnace
envisioned as a combination of a reverb with
a roaster in which smelting takes place simul- An important feature of the flash smelter is
taneously. Figure 15 shows a Outokumpu flash the concentrate burner, which suspends the feed
furnace designed in 1988 for smelting more than particles in the oxygen-enriched air in the hot
3000 t/d of copper concentrate – a production reaction shaft. The aim is to ensure a rapid, uni-
rate several times higher than those of earlier form (over the shaft, to prevent hot spots), and ef-
furnaces. The current trend is towards even big- ficient concentrate oxidation and generate min-
ger units. The furnace is 24 m long, 7.5 m wide, imum flue dust. Older flash smelters have four
and 2 m high in the settling area. The hearth or burners, but nowadays a single burner is used
settler is equipped with oil or natural gas burn- because it is easier to control the burner param-
ers. eters. The burner (Fig. 16) consists of two con-
The reaction shaft is 6 m in diameter and 7 m centric pipes: a central pipe for the solid feed
in height. It is equipped with one concentrate and an annulus for the oxygen-enriched blast. In
burner. The gas off-take shaft is 9 m high and the inner pipe a distributor cone is installed to
has a diameter of 5 m. (All dimensions inside optimize the particle distribution [225]. The gas
the furnace, which is lined with chrome magne- velocity out of the burner is up to 200 m/s.
sia bricks.) The furnace has eight matte tapholes
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 blast air, the process has approached the princi-
basic sulfates of copper, lead, and zinc, as well ple of INCO flash smelting. On the other hand,
as some volatile compounds of arsenic, anti- newer developments aim at the production of
mony, bismuth, and selenium. Repeated recy- blister copper or white metal (75 – 80 wt % Cu)
cling makes it possible to enrich selected ele- from concentrates in only one vessel, thereby
ments for later extraction. The quantity of flue approaching continuous smelting and convert-
dust is between 4 and 10 % of the input. ing as in the Noranda process.

Process Control. Five main parameters have


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

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
Copper 29

the surrounding equipment, this process is suit- 5.5.3. KIVCET Cyclone Smelting
able for replacing old furnaces within existing
smelters. Developments in power-plant technology have
led to adoption of the cyclone principle by the
Operation. Dry concentrate and flux are fed metallurgical industry. The acronym KIVCET
continuously to the Inco furnace. The products uses the initial letters of the following Russian
of the process are matte (50 – 60 % Cu), slag, and terms: oxygen, vortex, cyclone, electrothermic.
off-gas with 70 – 80 % SO2 . The slag is tapped at The development began in 1963, and the first
the sidewalls of the furnace, and the matte in the plant was operated by Irtysh Polymetal Com-
middle part under the offtake. The temperatures bine in Glubokoe, Kazakhstan. The process is
are similar to those of the Outokumpu furnace. not widely used for copper smelting.
In contrast to an Outokumpu furnace the amount The method is aimed at processing copper
of energy which is removed with the off-gas is sulfide concentrates that contain considerable
much lower because of the small off-gas quan- amounts of other metals. The essential part of
tity. Therefore the Inco furnace is not equipped the continuously operated plant is the smelt-
with a waste-heat boiler for energy recovery. The ing cyclone, in which the concentrates are fed
off-gas is cooled by different techniques such vertically, and technical-grade oxygen (95 %)
as splash towers, cyclones, or scrubbers [229]. is blown in horizontally, so that reaction takes
The absence of a waste-heat boiler avoids out- place rapidly above 1500 ◦ C.
of-service times of the furnace. Furthermore, the The furnace is divided to allow separating and
copper content in the slag of the Inco furnace is settling of the reaction products, in this respect
lower (0.5 – 1.5 %), and a slag-cleaning furnace similar to a reverb. In contrast to the separa-
is not needed. Only Hayden Smelter operates an tion chamber, the atmosphere in the electrically
additional electric furnace. Some operating data heated settler is maintained in a reducing state so
of the Chino, New Mexico furnace are listed in that the slag does not need special posttreatment.
the following: The off-gas volume is small, and the content
of SO2 can be up to ca. 80 %. Metals are reco-
Furnace commissioning date 1984 vered from the flue dust of both the separating
Size, inside brick, m hearth w × l × h 5.6 × 23 × 5 chamber and the settler. Table 13 and Figure 18
gas-off take w × h 3.9 × 7.7
Concentrate throughput, t/d 1520 explain the process.

Blast temperature, C 40
Oxygen enrichment, % 98 Table 13. KIVCET process: analysis and yield [84]
3
Blast flow-rate, m /h (STP) 12 500
Matte grade, % Cu 58 Analysis and yield Metal
3
Off-gas volume, m /h (STP) 20 000
SO2 Content 75 Cu, wt % Zn, wt % Pb, wt %
Recycling of converter slag in flash furnace
Slag treatment discarded Analysis
Fossil fuel input 0 Concentrate ∗ 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
Process Control. The aim of running the In oxidic condensate – 71.0 34.1
Inco furnace is the same than the Outokumpu
∗ Also 24.0 % Fe and 33.0 % S.
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 5.5.4. Contop Matte Smelting
oxygen enrichment is not adjustable. This could
be done by adjusting the mix of the feed (high Using a KIVCET license, KHD Humboldt
or low in copper) or adding fossil fuel for oxy- Wedag AG, Cologne developed the combined
gen consumption. But this is in conflict with the Contop process [85]. Contop stands for continu-
principle of the process and does not seem eco- ous smelting and top blowing. It is a combination
nomic.
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 The blister copper contains < 0.1 wt % S, ca.
0.5 wt % O, and traces of other impurities.
2 FeO + SiO2 −→ Fe2 SiO4
Converter Slags. The slags from the first
Formation of magnetite occurs near the tuyeres: step are iron(II) silicates (40 – 50 wt % Fe) with
high magnetite content (15 – 30 wt % Fe3 O4 ).
3 FeS + 5 O2 −→ Fe3 O4 + 3 SO2
The initial copper content of 3 – 8 wt % can in-
Copper(I) sulfide is partially oxidized, but it is crease up to 15 wt % at the end of the reaction
also reformed by formation of copper(I) oxide. This slag can
32 Copper

be decopperized by returning it to the smelting may be in the range of a thousand. More


unit or by froth flotation (cf.page 28). than 80 % of the worldwide produced cop-
The high-viscosity small-volume converter per comes from this type of converter. It is
slags from the second step have a high copper a horizontal cylinder lined with basic bricks
content (20 – 40 wt %) in the form of copper(I) (magnesite, chrome – magnesite) that can be
oxide or silicate. When enough slag has accumu- rotated about its long axis (Fig. 22); blast air
lated, it is returned to the first converting stage. is blown through a horizontal row of tuyeres.
In practice, the punching of tuyeres with spe-
Temperature. Converting is a strongly cial devices is necessary to maintain the flow
exothermic process that can overheat during of air. The largest vessels are 12.5 m long
oxidation of iron-rich mattes. The temperature with a diameter of 4.6 m.
must be held ca. 1200 ◦ C by adding fluxes, cop- 2) Hoboken or syphon converter [91]. This vari-
per scrap, precipitates from hydrometallurgical ation of the P – S type was developed years
treatment (e.g., cement copper), or concentrates. ago by Metallurgie Hoboken N.V., Belgium,
The off-gas (5 – 10 vol % SO2 ) is transferred to but is now used by only a few smelters in Eu-
a sulfuric acid plant. rope and in North and South America; larger
The blowing time per batch is a few hours; units are operated at Glogow smelter in Sile-
however, as the copper content of the matte in- sia, Poland; Cyprus Miami Smelter in Ari-
creases, the converting time decreases. Occa- zona; and Paipote smelter (ENAMI), Chile
sionally, oxygen-enriched air is used to increase [92]. Its advantage is its freedom from suck-
the throughput. ing in air, so the off-gas can attain SO2 levels
up to 12 %. Special features of the design are
Impurities. The distribution of other ele- the small converter mouth and the syphon or
ments among the phases during converting is as goose neck that guides the off-gas and flue
follows: dust flow.
3) Inspiration converter [93]. The vessel has two
1) Noble metals and most of the nickel, cobalt, mouths, the smaller for charging, the larger
selenium, and tellurium collect in white for the off-gas. The latter is well hooded in
metal and then in blister copper. all operating positions. It is only in operation
2) The bulk of zinc and some nickel and cobalt at Cyprus Miami Smelter.
collect in converter slag. 4) Top-blown rotary converter [95]. The TBRC,
3) The oxides and sulfates of arsenic, antimony, which is known in the steel industry as the
bismuth, tin, and the basic sulfates of lead are Kaldo converter, was adopted by the nonfer-
found in flue dust. rous industry (first by INCO, Canada) be-
cause of its great flexibility. Air, oxygen-
Converter Types. The copper converter was enriched air, or on occasion, commercial
invented in 1880 by Manhès and David, based oxygen is blown through a suspended water-
on the Bessemer converter, which had been used cooled lance onto the surface of a charge
in the steel industry since 1855. This develop- of copper-containing materials. In practice,
ment led to the incorrect name “copper besse- the TBRC is used batchwise for special op-
merizing,” although the true Bessemer process erations on a small scale, but generally not
is a refining step. Originally, the copper con- for converting copper matte. Tests of direct
verter was upright, and such obsolete units were smelting of concentrates (clean, complex,
in operation until the early 1980s, e.g., the Great or dirty) to white metal or blister copper
Falls converter developed by Anaconda Mining were performed at Rönnskär smelter (Boli-
Co., United States. den Metall AB), Sweden, but the process was
The following types are in use currently not realized technically. Copper extraction
(Fig. 21): from copper scrap and other secondary ma-
terials is also carried out. The TBRC is also
1) The Peirce – Smith converter has been the well suited for lead/precious metals metal-
most important apparatus for converting for lurgy.
many decades, and the number in operation
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 One of the problems of Peirce – Smith con-
and Environmental Protection To increase the verters is leakage SO2 -containing off-gas during
productivity of a Peirce – Smith converter, usu- charging and pouring operations in the working
ally the oxygen enrichment in the blast is in- environment. To avoid these fugitive emissions,
creased. Depending on process step (slag or cop- special secondary hooding systems have been
per blowing) up to 30 % O2 is used. The resulting developed and installed. For example, Figure 24
increases in the temperature in the vessel must be shows the hooding system used at Norddeutsche
controlled. Copper smelters mostly in Europe or Affinerie. The collected fugitive gases are dilute
Japan add copper scrap during the copper blow in SO2 (up to 0.2 %) and are treated by vari-
phase to adjust the temperature in the converter ous techniques (scrubbing with basic solutions
bath. Special systems (lift and conveyor) have or dry absorption of the SO2 producing gypsum)
been developed to add up to 70 % of the cooling [237], [238].
material without stopping blowing [232], [233]
(Figure 23).
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
Figure 23. Machine for automatic charging of cooling ma- and the Kennecott/Outokumpu Flash converting
terial process. Noranda has developed a continuously
Automatic temperature measurement (opti- running converter which has been in operation
cal spectrometer or thermocouple through the since 1997 at Horne Smelter.
tuyere) is used for process control and to avoid
high erosion of the brick lining of the con- 5.7.1. Noranda Process
verter. Also the chemistry of the converting
process is monitored by optical spectrometry In the 1970s Noranda started with the Noranda
[234]. This allows the blowing time to be easily reactor for directly smelting blister. This was
controlled without overblowing the charge and not useful and was therefore switched to smelt-
thus minimizes the copper loss to the converter ing high-grade matte. A second reactor similar
slag and magnetite formation in the slag. High- to the smelting one is proposed for continuous
velocity tuyeres have been developed [235], conversion of matte (patented 1985 [239]). Since
[236] which can be operated with high oxygen 1997 it has been operated at Horne smelter. It is
enrichment without extensive refractory ero- a horizontal cylindrical vessel with two mouths
sion. At the front of the tuyere a tubular accre- (one for adding liquid matte by ladle, the other
tion is formed which protects the brick lining. for the off-gas) and a row of submerged tuy-
Another advantage is that these tuyeres need not eres. There is also the possibility to feed solid
be punched (saves labor and maintenance cost). matte or coal by slinger belt through one end
A disadvantage is the relatively high pressure of wall. The converter is usually fed with liquid
about 3 bar of compressed air (high investment). high-grade matte (70 % Cu) from the Noranda
These high-velocity tuyeres have been tested in smelting reactor. It produces semi-blister cop-
Peirce – Smith and Hoboken converters. Today per with high sulfur content (1 – 1.5 %). The
(ca. 2000) the first smelters (Hidalgo) are plan- semi-blister is poured into a ladle which is trans-
ing to install the system. ported by special ladle car to the anode furnace.
The Noranda converter can be operated in four
Copper 35

Figure 24. Hooding system for the prevention of fugitive emissions at Norddeutsche Affinerie

modes: with molten matte feed, with any com- verter slag, copper scrap, and flue dust are
bination of solid and molten matte feed, up to smelted in this furnace. The fine material
100 % solid feed, in smelting mode with concen- (concentrate, coal) is fed through nine or
trate like the Noranda reactor and a conventional ten vertical steel lances on the top of the
Peirce – Smith converter. The converter at Horne molten bath. The blowing lances consist
Smelter (Figure 25) [240] is 4.5 m in diameter of two concentric pipes. Through the inner
and 19.8 m long (inside the brick lining). It has pipe, the dried concentrate is air blown, and
42 tuyeres. The process off-gas is collected in a through the outer one, oxygen-enriched blast
water-cooled hood and sent to the sulfuric acid (40 – 50 % O2 ). The lances are rotated to pre-
plant. The converter has a secondary ventilation vent them sticking in the roof. They extend
system, the gases of which are sent directly to to 0.5 – 1 m above the molten bath. About
a stack. This process operates continuously and 0.3 – 0.5 m of the lance is consumed each day.
has very high flexibility but not all of the poten- The off-gas contains 30 – 45 % SO2 and is
tial benefits have been achieved. There is still sent to sulfuric acid production.
crane transport and handling with ladles which 2) Slag-cleaning furnace: Slag and matte from
causes fugitive emissions. the S-furnace flow continuously by grav-
ity into the elliptical slag-cleaning furnace,
which is an electric furnace with three or
5.7.2. Mitsubishi Process six submerged graphite electrodes. The tem-
Mitsubishi Metals Corp., Japan, tested the perature of the slag is kept at 1250 ◦ C.
new concept during the 1960s and started the The slag is decopperized to 0.6 – 0.9 % Cu
first commercial plant at Naoshima smelter in and discarded. The matte flows continuously
1974. Today (ca. 2000) four companies are op- through a siphon into the converting furnace.
erating this process (Naoshima, Japan; Kidd 3) Converting or C-furnace: The matte (68 %
Creek, Canada; LG Metals, Korea; Gresik, In- Cu) is converted continuously by blowing
donesia). The principle of this process is the in- enriched air (30 – 35 % O2 ) and CaCO3 flux
terconnection of three furnaces, as shown in Fig- through six lances on the top of the bath. Also
ure 26 [241], [242]: copper scrap is added through the sidewall
of the furnace. Conversion only takes place
1) Smelting or S-furnace: Dried concentrates,
where the oxygen comes into contact with the
flux material, pulverized coal, return con-
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
Copper 37

Figure 26. Mitsubishi process

5.7.3. Kennecott/Outokumpu Flash est in the world. This is achieved because it has
Converting Process almost no fugitive emissions. The disadvantage
is that no scrap can be added to the converter.
In the 1980s Kennecott announced the develop-
ment of their Solid Matte Converting (SMOC)
process [244]. This process is based on solidify- 5.8. Direct Blister Smelting
ing the molten matte from the smelter, grinding,
and feeding the solid to an high-oxygen blast Normally copper extraction takes place in two
converter. This process decouples the smelting steps – concentrate smelting and matte convert-
and converting steps and gives great flexibility. ing – in which the chemical reactions are prin-
Later on, it was developed with Outokumpu, and cipally the same: oxidation of Fe and S. It has
for the converting step also a well-proven flash long been the aim to combine these processes
furnace was chosen. In 1995 the process went in a single step/reactor and minimize the en-
into operation at Garfield Smelter. ergy consumption and operating cost. Today (ca.
For matte smelting a flash furnace with a con- 2000) direct blister smelting is carried out at two
centrate feed rate of about 140 t/h was built (oxy- smelters (Glogow, Poland and Olympic Dam,
gen enrichment 65 – 75 %). The liquid matte Australia) in a Outokumpu flash furnace. Be-
contains 68 – 70 % copper and is granulated in tween 1973 and 1975, Noranda also used their
water. In the second step the matte is milled and reactor for blister smelting from concentrate, but
then fed together with lime as flux material to it was switched to matte smelting because of
the flash converter, which operates with an oxy- impurity problems. Another proposal is the QS
gen enrichment of 65 – 75 % O2 . The feed rate process.
of matte is about 60 t/h (up to max. 80 t/h) [245].
This furnace is constructed like the smelting fur-
5.8.1. Blister Flash Smelting [246]
nace. A blister copper and a calcium ferrite slag
with about 18 % copper (like in the Mitsubishi This process takes place in a conventional Out-
process) is obtained. The slag is granulated and okumpu flash smelting furnace. Concentrate and
fed back to the flash smelter. silica flux are fed with 60 – 85 % O2 blast to
The off-gases contain > 30 % SO2 and are the burner. The amount of O2 is just enough to
converted to sulfuric acid (input concentration of form blister copper. In practise, the particles in
14 % SO2 in the sulfuric acid plant). This process the reaction shaft are somewhat over-oxidized
has very low SO2 emissions of only 3.5 kg SO2 on the outside and incompletely oxidized on the
per tonne of copper, which is until now the low- inside. In the molten bath layers the reaction is
38 Copper

completed to form blister copper and iron silica recycled over and over again without losing its
slag. Formation of a layer of matte between blis- chemical or physical properties.
ter and slag must be avoided, because otherwise The processes used for copper recycling de-
a pronounced foaming reaction could take place. pend on the copper content of the secondary
In both operations copper concentrates with raw material, its size distribution, and other con-
low iron content (e.g., chalcocite, bornite) are stituents (Table 15) [249], [250]. Three general
processed to minimize slag production and cop- types can be defined:
per loss in the slag. The slag has a high cop-
Type
– 1: copper scrap (new and old scrap), used
per content (15 – 21 % Cu), mainly in oxidized
for smelting and refining or direct smelting
form, and has to be reduced in an electric fur-
for products. This type accounts for about
nace (produces copper – iron – lead alloy [247])
95 % of all recycled copper. The value of the
or concentrated by grinding and flotation. Re-
metal is much higher than its treatment costs.
duction in an electric furnace with addition of
Type
– 2: copper-containing special scrap such as
coke takes about 12 h residence time. The fur-
cables and printed circuit boards. Pretreat-
nace is operated at higher temperatures than the
ment (e.g., cable comminution) is necessary
normal flash smelter (slag temperature 1300 ◦ C)
before smelting the copper. Another example
to obtain higher solubility of magnetite in the
is copper in cars. Each car contains 10 – 30 kg
slag and decrease the viscosity of the slag. The
of Cu which must be separated from the iron.
blister copper contains 0.3 – 1 % S. At the Glo-
The value of the material is in the range of
gow Smelter, the process has been in operation
the overall treatment cost.
since 1977 with a daily throughput of 1500 t of
Type
– 3: copper-containing residues, for exam-
concentrate. At Olympic Dam it has been oper-
ple sludges from metal-plating industry. The
ated since 1988 and was enlarged in 1998.
copper content of these materials is low. The
value of the copper is much lower than the
5.8.2. QS Process treatment cost of the material.
High-purity secondary copper material is
The QS process, based on the QSL leadmaking used for smelting and casting new products, and
process, was invented by Queneau and Schuh- no fire and/or electrolytic refining is necessary.
mann in 1974 [109]. Blister copper is produced This is also true of pure alloy scrap, which is
from concentrate in a single vessel. The reactor used for fresh alloy. With increasing impurity
is similar to the Noranda reactor but has counter- content, the material is fed to smelting and refin-
current flow of slag and matte. Gases are injected ing processes. The process steps and aggregates
from the bottom [248] of the vessel to oxidize of secondary smelters are generally similar to
Fe and S and to reduce the copper content in the those of primary production, but the secondary
slag (Figure 27). Although the process has fun- raw material is usually metallic or oxidic [253].
damental and technical merits, it has not been Therefore, mainly reducing conditions are used
realized in a commercial plant. for secondary smelting. Often carbon in the form
of coke or natural gas is used.
For smelting metallic scrap, often shaft fur-
5.9. Copper Recycling naces (Asarco type or Contimelt) are used. For
smelting oxidic materials, blast furnaces, elec-
Most copper (> 95 %) is used in metallic form, tric furnaces, TBRCs, and Isasmelt furnaces are
as copper metal or copper alloys. Recycling of used. In the TBRC both the smelting and the
copper and its alloys has been carried out since converting step could be done. This saves en-
ancient times. In 1997, 37 % of copper consump- ergy in comparison with the blast furnace and
tion came from recycled copper. This low figure Peirce – Smith converter. In some cases electric
could be explained by the long lifetime of cop- arc furnaces are used instead of the blast fur-
per products (e.g., more than 30 years for copper nace. The advantage is that this furnace produces
wire) and the much increased copper production about 80 % less off-gas than the blast furnace.
in the last 50 years. Virtually all products made This makes the capture easier and more efficient.
from copper can be recycled, and copper can be
Copper 39

Figure 27. QS process


Table 15. Overview of different sorts of secondary copper sources

Type Material Cu content, % Source Recycling process

1 mixed copper scrap 90 – 95 sheets, gutters, water boilers, heaters, converting, fire refining
wires, pipes
1 pure copper scrap 99 semi-finished products, wire, strip, melting and casting of semifinished
cuttings products
1 red brass scrap 75 – 85 valves, taps, machine components, converting or alloy production
fittings, bearing boxes, car radiators
2 shredder material 60 – 65 cars blast furnace, electric furnace, TBRC
2 cable 40 – 50 buildings, cars shredder, firerefining
2 electronic scrap 10 – 20 electronics converting, TBRC
3 sludges 5 – 10 electroplating blast furnace, Electric furnace
3 copper – iron material 10 – 20 armatures, stators, rotors blast furnace, electric furnace, TBRC
3 drosses, ashes, slags 20 – 25 foundries blast furnace, electric furnace, TBRC

A typical flow sheet of a secondary smelter is results from sulfuric acid leaching of copper ore,
shown in Figure 28. which is combined with solvent extraction and
Many primary smelters treat scrap besides electrowinning. Other proposed techniques like
their internal recycling materials like anode ammonia leaching or hydrochloric acid leaching
scrap from the tankhouse or converter flue dusts. have minor importance. They are mainly pro-
Additional copper scrap bundles are fed to the posed for treating concentrates. A typical flow
Peirce – Smith matte converter. The scrap cools sheet of a sulfuric acid leaching operation is
the converters and uses the energy from matte shown in Figure 29.
oxidation for heating and melting.
Also electronic scrap such as printed circuit Chemistry Of Sulfuric Acid Leaching
boards is fed to copper matte converters (e.g., Processes. There are two chemically different
Norddeutsche Affinerie [251], [252]) or No- classes of copper minerals:
randa reactors (e.g., Noranda). The copper and
the precious metals are captured and sent to sub- 1) Oxidic or secondary minerals like malachite
sequent refining. The organic polymers are burnt and chrysocolla
at the high temperatures, and water and CO2 are 2) Sulfidic or primary minerals like chalcopy-
formed; ceramics are slagged. Because of the rite and chalcocite
high temperature and the high SO2 content in
The sulfidic minerals are the most common in an
the off-gas, no dioxins are formed.
ore body. Oxidic minerals are often located on
the top of the ore body and are present in smaller
amounts.
5.10. Hydrometallurgical Extraction Chemical reactions during extraction of cop-
About 15 % of the primary copper production per from primary and secondary minerals are as
in the western world, that is, about 1.8 × 106 t/a, follows:
40 Copper

Figure 28. Flow sheet of a secondary smelter

Figure 29. Sulfuric acid leaching of copper ores


Copper 41

Oxidic secondary copper minerals: metal is generated by electrolysis of the enriched


solution. After several months (1 – 6), leaching
CuCO3 · Cu(OH)2 + 2 H2 SO4 −→ is stopped and a new heap is placed on the top
2 CuSO4 + 3 H2 O + CO2 of the previous and leaching is begun again.
Data from a typical heap leaching plant are
Sulfidic primary copper minerals:
shown in Table 17. To produce 54 000 t/a of cop-
First step: generation of Fe3+ , which is the
per, 27 000 t ore per day must be treated.
oxidant for copper leaching, by bacteria.
Thiobacillus thiooxidans: Table 17. Typical data of heap and dump leaching operation

Heap leaching Dump leaching


2 FeS2 + 7 O2 + 2 H2 O −→ 2 FeSO4 + 2 H2 SO4
Cu cathode production, t/a 54 000 6600
Thiobacillus ferrooxidans: Leach ore composition chrysocolla 95 %
chalcopyrite, 3 %
2 FeSO4 + 0.5 O2 + H2 SO4 −→ 2 Fe3+ + 3 SO2−
4 + H2 O
chalcocite
Soluble Cu in ore, % 0.54 0.15
Second step: attacking the chalcopyrite: Total area under leach, m2 200 000 300 000
Tonnes of ore per day 27 000 55 000
Annual Cu recovery rate, % 90 20
2 Fe2 (SO4 )3 + CuFeS2 + 3 O2 + H2 O −→ Sulfuric acid consumption, 1.7 0
t/t Cu
5 FeSO4 + CuSO4 + 2 H2 SO4

Secondary minerals are readily soluble in sulfu- The copper production of a typical dump-
ric acid, and reaction times are typically short. leaching operation is much lower, for example.
After several hours most of the copper is ex- 6600 t/a. The feed material is very low grade sul-
tracted, but sometimes the ore requires a few fidic ore, and several years are required to extract
weeks reaction time. Recovery of copper from all the copper. The sulfuric acid consumption
primary minerals is more difficult because the depends on the mineralization of the copper ore
sulfides are very stable, and apart from sul- and the composition of the host rock. Typical
furic acid an oxidant is required as well. The figures are in the range of 1 – 5 t of sulfuric acid
most important oxidant is Fe3+ , which is gener- per tonne of copper product.
ated from the mineral chalcopyrite by bacteria- Minor methods are in situ leaching, tailings
assisted reactions with atmospheric oxygen. Al- leaching, and vat leaching. Vat leaching was
though these bacteria, which normally exist in carried out in the past to produce a pregnant
the mine water, speed up the process, very long leach solution with about 30 g/L Cu which was
reaction times like months or years are still nec- directly suitable for electrowinning. This tech-
essary to extract most of the copper. The con- nique is replaced by heap leaching and SX. Agi-
sumption of sulfuric acid depends on the type of tation leaching is used mainly to leach oxidic Cu
copper mineral. The bacterial leaching process concentrates in Zaire and Zambia. Fine particles
produces sulfuric acid itself. are treated with strong sulfuric acid (ca. 60 g/L)
solution, and the reaction is complete after sev-
Industrial Leaching Processes. The copper eral hours.
leaching techniques in practical use are listed in
Table 16. Other Leaching Processes. Mainly for the
The most important technique is heap leach- leaching of sulfidic copper concentrates, many
ing. It is very common for oxidic copper ore. The processes have been developed.
typical copper content is between 0.25 and 1 %. The Arbiter/Escondida Process was devel-
The ore is crushed to 1 – 10 cm and stacked to oped for leaching mainly chalcocite concen-
heaps 3 – 10 m high with an area of about 10 000 trates. In ammonia solution, half of the copper
to 100 000 m2 . Dilute sulfuric acid is sprayed on is extracted very quickly and CuS remains in the
the top of the heap. The liquor trickles through residue.
the material, copper is dissolved, and the copper-
bearing solution (1 – 5 g/L Cu) is collected at the Cu2 S + 2 NH3 + 2 NH+
4 + 0.5 O2 −→
bottom of the heap. This copper solution is puri- CuS + [Cu(NH3 )4 ]2+ + H2 O
fied and enriched by solvent extraction. Copper
42 Copper
Table 16. Common techniques for sulfuric acid leaching of copper mine

Leaching technique Mineralization % Cu in ore Leaching time Estimated Cu production


(1998), T/A

Heap oxides, chalcocite 0.25 – 1 several months to years 700 000


Dump chalcopyrite < 0.25 1 – 5 decades 50 000
In Situ all > 0.5 decades 50 000
Vat oxides 1–2 5 – 10 d 50 000
Agitation oxides (carbonates) 20 – 40 2–5h 200 000
Tailings oxides (carbonates) 0.25 – 1 1d 100 000

The reaction takes place in agitated vessels. The residue can be treated with cyanide for gold re-
copper complex solution is sent to a solvent ex- covery. This process was tested in laboratory
traction and electrowinning plant. The residue scale. It might find use for impure concentrates
is sent to a flotation plant, where copper is en- or concentrates high in precious metals.
riched, and then fed to a smelter. This process Bacterial leaching of chalcopyrite concen-
was operated at Escondida mine in Chile but at trates (Bio COP) is developed since 1997 at
present is shut down. Codelco’s Chuquicamata mine. The sulfide con-
The Cuprex process uses iron(III) chloride centrate is leached in stirred tanks at 65 – 85 ◦ C
for the oxidation of copper from chalcopyrite: assisted by special heat-resistant bacteria (bac-
teria mesofila). The process needs large amounts
CuFeS2 + 4 FeCl3 −→ CuCl2 + 5 FeCl2 + 2 S of air/oxygen. The copper sulfate solution is fed
to a SX-plant and then to copper electrowinning.
A solvent extraction step gives pure CuCl2 so- A pilot plant will be built within the next 2 years.
lution (ca. 100 g/L Cu), which is fed to a mem-
brane-divided electrowinning cell, where cop- Solvent Extraction. The pregnant leach so-
per powder is produced and in at the anode the lutions from heap, dump, or in situ leaching
iron(II) chloride is oxidized to iron(III) chloride are too dilute in Cu (1 – 5 g/L) and too impure
and recycled to the leaching process. The pro- for direct production of high-grade copper cath-
cess has been tested in a 1 t/d pilot plant. odes. Industrial copper winning requires elec-
The Intec process is carried out in a trolytes with about 40 – 50 g/L copper. Copper
NaCl/NaBr solution at 80 – 85 ◦ C with CuCl2 enrichment and purification, mainly to remove
as oxidant. Leaching is carried out in four steps; iron, is done by solvent extraction. The dilute,
gold is also leached in the last step. The residue impure solution from the leaching operation is
consists of Fe(O)OH and elemental sulfur. mixed with an organic solution, which is based
on kerosene or petroleum and contains about
4 CuFeS2 + 4 CuCl2 + 3 O2 + 2 H2 O −→
5 – 10 % of an extractant which is selective for
8 CuCl + 4 FeOOH + 8 S copper. The organic extractants used for the pro-
The solution is cleaned by adding CaO and then cess are salicylaldoximes and ketoximes (RH)
sent to a membrane electrolytic cell. At the cath- and commercially available as LIX (Henkel) or
ode copper is reduced to copper powder. At the MOC (Allied Signal). The copper ions are com-
anode two reactions take place: oxidation of Cu+ plexed by these reagents and enter the organic
to Cu2+ and oxidation of bromide ions to BrCl− . phase:
This solution, which contains about 30 g/L Cu,
2 RH + CuSO4 −→ R2 Cu + H2 SO4
is sent back to the leaching reactor (step 4, Au
leaching). After mixing, the aqueous and organic phases
Oxygen pressure leaching of chalcopyrite, are separated by gravity (settler). In a second
bornite, or chalcocite concentrates in sulfuric step, copper is stripped from the organic phase
acid under 8 bar oxygen pressure at 200 ◦ C gives with more highly concentrated sulfuric acid so-
about 99 % copper recovery after a short reac- lution.
tion time of only one hour. The dissolved copper
can be recovered by electrowinning. The leach H2 SO4 + R2 Cu −→ 2 RH + CuSO4
Copper 43

Normally, the depleted solution from elec- recovered from low-grade materials which are
trowinning, which contains about 170 g/L unsuitable for smelters. With improvements in
H2 SO4 and 35 g/l Cu, is used. It is enriched solvent extraction and electrowinning technol-
with copper to about 50 g/L and sent to the elec- ogy, the quality of the recovered copper has be-
trowinning cells. Depending on the composition come as good as that from classical refineries.
of the dilute solution from the leaching plant sev- Leaching facilities are mostly located at the cop-
eral mixer/settler steps are needed for purifica- per mines. The disadvantage of leaching is that
tion of the copper. it does not recover the precious metals.
Production figures (in 103 t/a) for L/SX/EW
Copper Electrowinning. The copper- copper by region in 1997 follow:
enriched sulfuric acid solution (ca. 40 – 50 g/L
Cu, 140 – 170 g/L H2 SO4 ) is sent to the elec- North America 567
trowinning cells, which are similar in construc- Latin America 943
Oceania 49
tion to refining copper cells. Copper is depleted Africa 65
at the cathode on stainless steel sheet (ISA Pro- Asia 4
cess) or copper starters. The cathode reaction is Western Europe 2
identical to the refining reaction:
The expected growth of western world copper
Cu2+ + 2 e− −→ Cu E 0 = 0.34 V production and the contributions from smelters
The anode reaction is completely different. In- and L/SX/EW operations is shown in Figure 30.
ert anodes, mainly PbSnCa alloy, are used, and Copper production is expected to increase from
oxygen is formed at the anode. about 12 × 106 t/a in 1996 to about 14 × 106 t/a
in the year 2000. The biggest part of this growth
H2 O −→ 0.5 O2 + 2 H+ + 2 e− E 0 = 1.23 V will come from L/SX/EW operations. Smelter
The electrical potential needed for copper production will also increase, but there the next
electrowinning is about 2 V, as opposed to step in capacity enlargement is expected after
about 0.3 V for copper electrorefining. About 2002.
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-
Figure 30. World copper production statistics
ities up to 200 000 t/a of cathode copper.
Most of the increase in copper production by
Economics of Copper Production by leaching was accounted for by Latin America
L/SX/EW Processes Compared with copper (Figure 31). By 2002 or 2003, the production of
production in smelters, L/SX/EW processes L/SX/EW copper is expected to have increased
have lower production figures. But the argu- by nearly a factor of three. Several new opera-
ments for the L/SX/EW techniques are low in- tions are scheduled for the near future.
vestment costs and increased copper output ef-
ficiency of mines. Furthermore, copper can be
44 Copper

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.
Figure 31. Copper production by the L/SX/EW technique 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
6. Refining efficient. An extra melting furnace, e.g., anode
shaft type (Section 6.1.2), can be required for
Conventional refining comprises three stages: remelting of solid materials (scrap and anode
(1) pyrometallurgical or fire refining, (2) elec- rests).
trolytic refining, and (3) remelting of cathodes Low-sulfur pulverized coal, fuel oil, natu-
and casting of shapes. Refining without elec- ral gas, or reformed natural gas serve as fuel.
trolysis is adequate if the fire-refined copper The refractory lining consists of basic bricks,
has the necessary purity and if the content of such as magnesite or the more spall-resistant
precious metals can be neglected. If extremely chrome – magnesite bricks.
high-purity copper is needed, zone melting or After charging and possibly melting, oxida-
repeated electrolysis of cathodes is used. 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
6.1. Pyrometallurgical Refining and partly volatilizing the impurities. During this
blowing step, a part of the copper is oxidized to
Fire refining is applied to crude copper such copper (I) oxide, which dissolves in the liquid
as blister copper from converters (ca. 97 – metal (Fig. 32). If the content of Cu2 O in cop-
99 wt % Cu), black copper from blast furnaces per increases to ca. 10 wt % (corresponding to
(ca. 90 – 95 wt % Cu), cement copper from hy- 1 wt % O), it acts as a selective oxidizing agent:
drometallurgical operations (ca. 85 – 90 wt %
Cu), anode scrap from electrolytic refining, and Cu2 S + 2 Cu2 O −→ 6 Cu + SO2
high-grade copper scrap, chiefly unalloyed wire
scrap. In practice, large amounts of SO2 are generated
The refining of molten copper to anode cop- so that this final stage of the oxidation period is
per for electrolysis or commercial fire-refined termed boiling. Reduction of the sulfur content
copper has the following functions: limits SO2 blisters in the solid copper.
The subsequent poling with wood is a
1) Removing impurities by slagging and centuries-old method that is still employed in
volatilization, with the precious metals re- older reverb plants. Large tree trunks (poles) of
maining entirely in the metallic copper beech, birch, eucalyptus, etc. are plunged un-
2) Reducing the sulfur content to ca. der the surface of the melt to generate reducing
0.0005 – 0.005 wt % by oxidation gases and steam by dry distillation of the wood.
The escaping gas mixture reacts with copper (I)
Copper 45

oxide and mixes the molten bath [1, p. 441], [2, the Cu – H – O system for the reduction or poling
p. 392]. period.
This awkward operation has been largely dis- When a copper melt solidifies, a shrinkage
placed by gas poling [143] in rotary furnaces: of ca. 5 vol % occurs, but a flat surface can be
natural gas (CH4 ), reformed gas (CO, H2 , and achieved by careful control of the equilibrium
N2 ), propane, or ammonia [144] is blown into
the copper melt through tuyeres. This process Cu2 O + H2  2 Cu + H2 O
has been introduced at most smelters in the The steam of micropores can compensate the
world. 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
Figure 32. Partial phase diagram of the Cu – Cu2 O system
been operated since 1982 on a commercial scale.
The poling operation proceeds in two steps. The continuous operations are performed suc-
During tight poling, the remaining sulfur dioxide cessively in two units connected by launders.
from copper (I) sulfide is almost entirely flushed First is the anode shaft furnace, where charg-
out by the escaping gas, a sample of liquid cop- ing, melting, and oxidation of crude copper take
per at the end of this stage solidifying without place. Second is the small drum-type furnace,
blisters or cavities. Next comes the poling tough where poling and casting of anodes are carried
pitch, which is necessary to reduce the copper (I) out. The oxygen content of copper from the an-
oxide and achieve the required low oxygen con- ode shaft furnace averages 0.6 %, with 0.15 %
tent. High Cu2 O content in the solidified metal after poling. A feature of the shaft furnace is the
causes brittleness and decreased strength; more- additional equipment with oxygen burners for
over, Cu2 O disproportionates to copper metal regulating the composition of the furnace atmo-
and copper(II) ions in sulfuric acid electrolytes, sphere and the overheating of copper. In com-
which disturbs the electrolytic refining opera- parison with conventional fire refining, the Con-
tion. timelt process provides savings in energy and
The final oxygen content in fire-refined tough labor.
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- 6.1.3. Casting of Anodes
tem [145] (see Fig. 32); the system Cu – O – S is
important in the oxidation period (see Fig. 5) and 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


The greater electrochemical equivalent of
About 80 % of the world copper production is copper (I) suggests the use of solutions of cop-
refined by electrolysis. This includes all primary per (I) ions instead of copper (II) ions. However,
copper and much secondary copper. This treat- this concept has not been put into practice be-
ment yields copper with high electrical conduc- cause of enormous industrial difficulties [151].
tivity and provides for separation of valuable im- The two most important electrical parame-
purities, especially the precious metals. ters in electrolytic copper refining operations are
The basic patent, GB 2838, for galvanic de- the cell voltage and the current density. The cell
position of metals was awarded to J. B. Elk- voltage, which usually ranges between 0.25 and
ington in 1865. The most important technical 0.3 V, is determined by several factors:
problems were solved by E. Wohlwill at the
1) Ohmic resistance of the electrolyte, depend-
Norddeutsche Affinerie in Hamburg, Germany,
ing on composition, temperature, electrode
in 1876, and this method has been used ever
distance, and cell construction
since. The first electrolytic copper refinery in the
2) Polarization, especially concentration polar-
United States was operated from 1883 to 1918 by
ization of electrodes, which depends on the
the Balbach Smelting and Refining Co., Newark,
rate of electrolyte circulation
New Jersey.
Copper 47

3) Overpotential because of organic additives 4) Prevention or elimination of suspended


(e.g., an inhibitor for achieving uniform elec- slimes by regulating the electrolyte flow and
trocrystallization of copper) occasionally filtering it.
4) Voltage loss in the circuit
5) Anode passivity, which may occur at high Electrolyte. The composition of copper elec-
current densities trolytes from various plants is generally simi-
lar: ca. 35 – 45 g of copper and 150 – 220 g of
The interaction of these effects is difficult to sulfuric acid per liter at an operating tempera-
predict. At any particular electrolytic facility, a ture of 55 – 65 ◦ C (see Table 14). As a result of
continuing effort is made to optimize parameters secondary reactions during electrolysis, the con-
that affect the cell voltage. The voltage loss in the centration of copper (II) ions increases slowly;
conductors and contacts is minimized by good therefore, this copper surplus must be recovered
plant design and use of special contacts (Bal- by cathodic deposition in a few (ca. 2 %) liber-
timore grooves, Whitehead contacts, wet con- ator cells equipped with insoluble anodes, usu-
tacts, etc.). ally of antimonial lead. Soluble impurities, such
The second important parameter is the ca- as iron, cobalt, zinc, manganese, most of the
thodic current density. With increasing current nickel, and some arsenic and antimony, are also
density the production of copper increases and enriched in the electrolyte.
the current efficiency decreases because the The upper limits of impurity content are ca.
cathode potential depends on the current den- 10 g/L for arsenic and 20 – 25 g/L for nickel.
sity. Part of the electrolyte is withdrawn continuously
from the circuit for purification, and the volume
Impurities. The behavior of impurities de- is compensated by adding sulfuric acid and cath-
pends on their position in the electrochemical ode wash water. There are two methods of pu-
series: elements more noble than copper are in- rification. In the first, the solution can be com-
soluble, while less noble ones dissolve in or re- pletely decopperized in a system of special lib-
act with the electrolyte. For that reason, the an- erator cells with insoluble anodes; arsenic and
ode material is distributed by electrolysis among antimony are almost completely deposited and
three phases: cathode copper, electrolyte, and returned to pyrometallurgical operations. The
anode slime (Table 18) [152]. Table 19 lists the electrolyte is then concentrated by vacuum evap-
fractions of anode elements that enter residues oration to yield concentrated sulfuric acid and
and electrolyte. crude nickel sulfate, from which pure nickel sul-
fate or nickel metal can be produced.
Copper Cathodes. Cathode copper is pro- The second method of purification is by pro-
duced currently in a purity between 99.97 and ducing copper sulfate. For this purpose, the sul-
99.99 %. Silver can be deposited in traces; how- furic acid is usually neutralized by addition of
ever, this can be avoided by precipitating the copper shot in the presence of air. The copper
silver from the electrolyte with chloride ion. sulfate is obtained by crystallization, and the
Other impurities, such as suspended slime or mother liquor is cemented with iron scrap.
droplets of the electrolyte, may be mechanically
occluded. The following measures are taken to Anode Slimes [153], [154]. The content of
produce copper of high purity: insoluble substances is < 1 % of the anode
1) Maintenance of the optimum current density, weight, and they collect on the bottom of cells
to prevent cathodic deposition of other ele- as anode slime. They contain precious metals
ments (e.g., arsenic) (silver, gold, and platinum); selenides and tel-
2) Addition of organic inhibitors to avoid the lurides of copper and silver; lead sulfate; stan-
formation of nodules on the cathode surface nic [tin (IV)] oxide hydrate; and complex com-
3) Removal of impurities such as arsenic, anti- pounds of arsenic, antimony, and bismuth (the
mony, and bismuth from the electrolyte by undesired floating slimes). The main component
adsorption or chemisorption 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-
Copper 49

trolyte in one cell is exchanged every 5 – 6 h, yielding an evenly grained copper deposition.
which is important for removing impurities from Important surface-active additives, or inhibitors,
the cell. are bone glue, gelatin, avitone A (sulfonated
The anodes remain in the cell for 20 – 28 d. aliphatic hydrocarbons), goulac, or bindarene
During this time the cathodes are usually (sulfonated wood fibers). Effective substances
changed two or three times, so that their weight with definite composition are thiourea and its
is only 60 – 160 kg. The cathodes are removed derivatives and other sulfur – nitrogen com-
by crane and the electrolyte on their surface is pounds. These inhibitors, mostly in combina-
washed off with hot water. In tankhouses which tion, are added to the electrolyte in extremely
use stainless steel sheets, the plated copper is small amounts, although more is added at higher
stripped mechanically (automatic stripping ma- current density. Inhibitors increase the voltage
chine) from both sides of the blank. In conven- and, therefore, the energy consumption. Several
tional tankhouses copper starter sheets are pre- refineries automatically control their reagent ad-
pared by electrodeposition of copper on titanium dition rates by measuring glue and thiourea, for
sheets (< 1 mm, about 1 d) in special stripper example, with the CollaMat [254–256] system.
cells. Then the copper sheets are attached to This stabilizes refinery operation and optimizes
rolled copper support bars for hanging in the the process (lower energy consumption).
cells. This process is partly mechanized [164].
About 15 % of the anode is not dissolved dur- Special Developments. Jumbo tanks instead
ing the refining process. This anode scrap is re- of conventional cells, first installed in 1972 at
cycled to the smelter (converter or shaft furnace). Onahama Tankhouse, Japan [165]. The jumbo
The anode slime of the complete cycle is drained, tanks have about 20 times the volume of con-
filtered, washed, and sent to the precious metal ventional cells. The electrolyte flows parallel to
plant. Part of the electrolyte is removed continu- the electrode surface, in contrast to conventional
ously from the circulation system for purifying. cells. A newer installation of jumbo tanks is the
The sulfuric acid is sent back to the tankhouse. Kidd Creek tankhouse in Canada.
To overcome anodic passivation caused by
Electrical System. The anodes and cathodes high current density and impure anodes a peri-
in a cell are connected in parallel. The cells are odic current reversal system (PCR) [166] was
connected in series to form sections of 20 to 40 developed. Optimum reversal conditions seem
cells. Each section can be isolated electrically to be 20 units forward time and 1 unit reverse
for inserting or removing anodes or cathodes. time [257]. This system has been adopted in
For example, 12 sections are connected with one some refineries, but due to the extra energy costs
silicon controlled rectifier for current input. To- it is not widely used.
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 6.3. Melting and Casting
obtain a high current efficiency of 92 – 98 %, the
bath and section voltages are monitored [254], Copper cathodes must be remelted and cast to
[255], and the temperature of the cells is mea- shapes because the structure of copper formed
sured by infrared techniques (from the crane). In by electrocrystallization is not suitable for work-
this way short circuits, caused, for example, by ing to semifinished products. Cathodes are
the growth of copper nodules can be quickly de- remelted in several types of special furnaces that
tected and corrected. The energy consumption perform the tasks of melting, postrefining (if
of electrorefining per tonne of plated copper is necessary), holding, and casting. Casting can be
about 260 – 280 kW h. carried out by the older discontinuous methods
or by modern continuous casting.
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
50 Copper

6.3.1. Remelting of Cathodes comprehensive synopsis, including patents, has


been published [171].
There are various kinds of furnaces that use ei- Continuous casting has several technological
ther fossil fuels (coal, coke, fuel oil, natural gas, and economic advantages over the older casting
or reformed natural gas) or electric energy: processes, such as excellent surface quality, uni-
Small coke-fired crucible furnaces form grain structure without blisters and shrink-
Gas- or oil-fired rotary furnaces age cavities, and energy savings.
Large hearth furnaces (reverbs) Molten copper flows continuously into a rel-
Electric-arc furnaces atively short water-cooled chill, usually lined
Low-frequency induction furnaces with graphite and open at both top and bottom.
Cathode shaft furnaces (e.g., ASARCO type) The solidifying metal itself forms the lower clo-
Copper ready for pouring must be nearly free sure. The shape is steadily withdrawn by clamp-
of sulfur, at most 10−3 % (10 ppm) S, because a ing rolls and cooled by spraying with water.
higher content affects detrimentally the mechan- There are three main continuously cast
ical properties of the metal. shapes: circular billets with a diameter up to
In practice, copper is treated in two ways: 500 mm (for extrusion presses or tube rolling
mills), square bars, and rectangular cakes with
1) After melting cathodes with sulfur- cross sections up to 1300 × 200 mm (for rolling
containing fuels, the copper melt must be to sheets and strips). Seamless tubes and other
fire-refined like blister copper, by oxidation hollow shapes are occasionally produced. Con-
and poling. This is the case when hearth tinuous casting shapes are automatically sawn
furnaces are employed for casting. off by flying saws when they reach the required
2) Use of electric power or sulfur-free fuels al- lengths (up to 7.5 m). In semicontinuous casting,
lows the use of continuous units, such as in- the process must be interrupted, but the shapes
duction or ASARCO furnaces. can be up to ca. 12 m long.
The ASARCO shaft furnace, constructed by The kind of chill is generally independent of
American Smelting and Refining Co. [168], the furnace: the liquid metal stream free-falls
[169], has a cylindrical shaft consisting of a steel into the chill (e.g., Junghans system), or the less
jacket with a brick lining. Cathodes are charged frequent fixed connection of chill with the fur-
near the top, and the combustion gases ascend nace (e.g., ASARCO casting system).
in countercurrent flow from groups of burners; Other methods employ a joint moving in uni-
the liquid metal is collected in a holding furnace. son with the solidifying metal and a mold with
Apart from its effectiveness and high productiv- traveling parts forming a gap of the required
ity, a distinct advantage is the maintenance of a cross section. (An example is the Hazelett pro-
constant, slightly reducing atmosphere by auto- cess employed for continuous casting of anodes.
matic control. The largest types (1.8 m diameter Section 6.1.3.) Such casting methods are par-
and 8 m high) can have a throughput up to 80 t/h. ticularly suitable for continuous production of
Worldwide ca. 200 units are in operation. shapes with a small cross section. Section 6.3.4.

6.3.2. Discontinuous Casting 6.3.4. Continuous Rod Casting and Rolling


The discontinuous casting of various shapes
on horizontal casting wheels with open ingot The continuous production of cast and rolled
molds, analogous to the casting of anodes, was wire rod [172], [173] involves considerable en-
formerly the most important casting method. It is ergy savings because the solidified hot metal can
being replaced by continuous casting processes. be rolled immediately. Several plants use such a
direct process starting from molten electrolytic
tough-pitch copper. Worldwide >100 plants are
6.3.3. Continuous Casting in operation, using the following systems:

Since the end of World War II, several contin-


uous casting methods have been developed. A
Copper 51

1) Properzi process [174]. The first continuous hot rolling is not required. Approximately 40
copper rod caster was constructed in 1960 plants are in operation.
following developments for other nonferrous
metals. It operates on the wheel – belt casting
principle, i.e., casting into the gap between 6.4. Copper Powder
the periphery of the casting wheel and the
closing steel belt. About ten plants are in op- Copper and copper-alloy powders are required
eration with a capacity up to 30 t/h. for products prepared by powder metallurgical
2) Southwire process [175]. Started in 1963 as a techniques, including friction materials, carbon
further development of the wheel – belt cast- brushes, self-lubricating bronze bearings, spe-
ing principle with capacity up to ca. 50 t/h, cial filters, and catalysts and other sintered com-
the Southwire process directly introduces ponents.
the continuous cast bar into the rolling mill The principal methods for producing cop-
(Fig. 33). After rolling, the rod, which is ox- per powders are electrolytic deposition at high
idized on the surface, is continuously treated current densities and the atomization of molten
by pickling with dilute sulfuric acid or alco- metal, the latter more for copper-alloy powders.
hols, water or steam rinsing, and wax coating. Copper powders are also formed by cementa-
The saleable product (8 – 20 mm diameter) is tion or by pressurized precipitation from aque-
formed into “coils” of up to 10 t, which are ous solutions, but such precipitates are of little
packaged. About 30 plants exist at present. commercial interest.
3) Secor process [177]. Only two factories Atomizing is done by spraying a melt into
(Australia and Spain) use this modified a pressurized air or water flow. Various grain
wheel – belt casting concept, dating from shapes are formed, depending on the cooling
1975, with a capacity up to ca. 10 t/h. rate and on additives that change the surface
4) Contirod or Krupp – Hazelett process [178]. tension. Additives that decrease surface tension,
As a variant of the Hazelett twin-belt pro- e.g., magnesium, form irregular powders; those
cess similar to the Contilanod process (Sec- that increase it, e.g., lead or phosphorus, yield
tion 6.1.3.), the continuous cast bar solidifies globular particles. Spongy powders can be ob-
between two belts and damblock chains and tained by reduction of oxidized copper powders
is directly moved to the rolling mill (Fig. 33). with hydrogen.
Metallurgie Hoboken-Overpelt, Belgium, Electrolytically deposited powder particles
developed this system in the 1960s; the ca- have dendritic shape; a typical flow sheet is
pacity of the largest units is ca. 50 t/h. At shown in Figure 34. For this purpose electrolysis
present about 20 plants are operated. is used as a shaping process rather than for refin-
5) General Electric dip forming process [179]. ing because high-purity copper cathodes are the
A process based on the “candlestick” prin- anodes. The main parameters of powder elec-
ciple has been operated since about 1970. A trolysis are, as Figure 35 shows, the following
copper core rod is pulled upward through liq- [181]:
uid copper so that its diameter increases; the
Cathodic current density
thickened rod moves immediately to rolling.
Electrolyte temperature
Oxygen-free copper can be produced by us-
Concentration of copper (II) ions
ing a reducing atmosphere. The capacity is
Concentration of chloride ions
ca. 10 t/h. Nearly 20 plants exist at present.
6) Outokumpu up-cast process [180]. A new Varying these factors markedly change particle
upward casting system developed in 1969 shapes and apparent densities.
draws copper upward through a vertical die Anodic and cathodic current densities dif-
cooler with a cooled graphite mouthpiece fer. The former is normally 300 – 600 A/m2 , and
dipping into the melt. The caster, compris- the latter is 2000 – 4000 A/m2 , which is 10 – 20
ing 8 or 12 strands, yields oxygen-free cop- times higher than the cathodic values in conven-
per at the rate of ca. 2 t/h per line. Because of tional electrolytic copper refining. This effect is
the small cross section (8 – 25 mm diameter), 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 Without regard to the method of refining,
powders are generally posttreated for various tough-pitch copper normally contains 0.02 –
purposes. Electrolytic copper powders are char- 0.04 wt % O (as Cu2 O) and ca. 0.01 wt % total of
acterized by dendritic particle shape, high purity, other impurities. This grade is easily worked and
low oxygen content, favorable resistance to ox- has an electrical conductivity of  100 % IACS,
idation, and good green strength. but it is unsuitable for welding and brazing be-
During the last 5 years the electrowinning cause of the danger of hydrogen embrittlement.
technology to produce copper powder was de- About 80 % of the world production of refined
veloped to commercial scale. By using pregnant copper is tough pitch, mostly electrolytic tough-
leach solution from ore leaching operation and pitch copper (ETP).
subsequent solvent extraction and electrowin- Deoxidized copper, with no oxygen content
ning in specially designed cells, it is possible is produced by addition of nonmetallic or metal-
to produce dendritic shape copper powder with lic reducing agents, usually copper phosphide.
well defined parameters like particle size [258]. As a result of the absence of oxygen, hydrogen
embrittlement cannot occur, and such copper is
well suited for welding and brazing. The con-
6.5. Copper Grades and tent of residual phosphorus, however, increases
Standardization the electrical resistivity. Deoxidized copper with
low residual phosphorus (DLP, ca. 0.005 % P) is
The three main grades of refined copper are (1) required if the metal is to be used as a conduc-
tough-pitch copper, (2) deoxidized copper, and tor. Copper with high residual phosphorus (DHP,
(3) oxygen-free copper.
Copper 53

Figure 35. Apparent density of electrolytic copper powder


as a function of four electrolysis parameters [181]
Figure 34. Flow sheet for electrolytic copper powder pro- Other conditions: A) Cu 6 g/L, no Cl, 60 ◦ C; B) Cu 17 g/L,
duction [181] no Cl, 3600 A/m2 ; C) no Cl, 50 ◦ C, 3600 A/m2 ; D) Cu
13 g/L, 50 ◦ C, 3600 A/m2

ca. 0.04 % P) can be employed for nonelectrical mensions, but differences exist. Table 20 indi-
purposes. cates the rough equivalent between international
Oxygen-free (OF) copper is a special qual- and European specifications for the most impor-
ity produced by keeping oxygen away from the tant copper properties.
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 6.6. Quality Control and Analysis
weldability and high electrical conductivity, es-
pecially electronics. OFHC, oxygen-free high- Tests for quality control of copper are carried out
conductivity copper, is internationally known. on samples of both refinery shapes and semifin-
ished products. There is need to standardize the
Standardization [14], [182], [183]. Most testing methods, but currently only some of them
industrial countries have established standards are fixed in national specifications. The most im-
for copper; these national specifications include portant tests are the measurement of electrical
detailed specifications for chemical composi- conductivity, mechanical properties, and qual-
tion, physical properties, and geometrical di- 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- cially important to analyze the oxygen content,
tive to impurities and crystal lattice imperfec- and one effective modernized method is avail-
tions. Mechanical tests measure hardness, ten- able, hot extraction, i.e., melting a copper sam-
sile strength, elongation at failure, and torsional ple in a small graphite crucible and determining
fatigue strength. The spiral elongation test [184] the CO formed by IR absorption spectroscopy.
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 7. Processing and Uses
in various forms, e.g., folds, splashes, cracks,
inclusions, and voids. The voids are caused by The pure metal produced in refineries or remelt-
gas porosity, shrinkage porosity, and shrinkage ing plants is manufactured into semifabricated
cavities. products.
Nondestructive testing procedures, such as
radiography, ultrasonic examination, or the
7.1. Working Processes
eddy-current technique can be used. Metallo-
graphic methods (polishing and etching) give Usually copper is treated initially by noncutting,
information by microscopic examination. shaping processes to obtain semifinished prod-
Analytical methods are of interest for de- ucts or “semis”. These processes are subdivided
termining the impurity level of copper prod- into hot working, cold working and, if necessary,
ucts. Both wet chemical procedures and phys- process annealing.
icochemical procedures, such as atomic ab- Hot working means plastic forming above the
sorption spectrometry, optical emission spec- recrystallization temperature. Generally copper
troscopy, and X-ray fluorescence spectroscopy, is preheated to 800 – 900 ◦ C, and the subsequent
are employed, the latter essentially for quick hot forming is finished at ca. 400 ◦ C. Cast bars
analysis of solid and liquid co- and byproducts from modern combined continuous casting/rod-
[185], [186]. The classical analytical methods rolling systems already have sufficient temper-
are gradually being superseded by the modern ature, thus saving thermal energy. After cool-
automatic instrumental techniques. It is espe- 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 installation, wall lining, and roofing. Hydraulic
is known as “hydrogen embrittlement.” engineers use copper sheets for tightening on
Mechanical joining and metal bonding are dams, sluices (floodgates), and bridges.
also possible ways of joining copper with other Other areas of application are in the fabrica-
materials. tion of household articles, art objects, coins and
Surface treatment of copper is a group of medals, and in military hardware as ammunition.
operations for surface protection or surface re- There is a smaller demand for other purposes,
finement. These include mechanical, electri- such as electrodeposition; powder-metallurgical
cal, or electrochemical handling, e.g., polish- copper, special materials for brakes and self-
ing, matte finishing, pickling by dilute sulfu- lubricating bearings, small precision parts, fil-
ric or nitric acid, metal coating or electroplating ters, graphite brushes; and alloying additives for
(with nickel, nickel and chromium, tin, silver, aluminum, iron, and steel. Use in copper com-
gold, or platinum metals), lacquering or coat- pounds, chiefly copper sulfate and copper ox-
ing with synthetic plastics (mainly for electrical ides, consumes only 1 – 2 % of the primary world
insulation), enameling of objects (applied art), production.
and chemical or electrochemical coloring (dec- Table 22 lists the distribution of copper con-
oration). Coloration is effected by chemicals, sumption among various industries.
mostly specially formulated metal salt solutions
Table 22. Industrial use of copper (including alloys) in the Western
which form thin layers of insoluble green, red, world in 1995, percentage by country [190]
brown, or black compounds.
Branch United Europe Asia
States

Electrical and electronic industry 25 37.5 50


7.3. Uses Industrial machinery and 11 9 9
equipment
Copper is a useful material with a wide range of Building construction 43 39.5 15
Transportation 9 6.5 11
applications because of its combination of prop- Consumer and general products 12 7.5 15
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- Substitution and Miniaturization. Several
mission, and conduction; various sorts of cables materials compete with copper and may sub-
are produced for special applications. Substan- stitute for it, depending on the relative costs.
tial quantities of copper are made into genera- Copper is partly replaced by aluminum in au-
tors, motors, transformers, and other electrical tomotive radiators and in transmission cables,
appliances. About 40 % of the world consump- high-voltage long-distance lines, and household
tion of copper is for electrical purposes. As a wiring. Copper wires and cables for telecom-
result of its high thermal conductivity, copper is munications are being displaced by microwave
well-suited for vessels and pipes, especially for technology and fiber optics. Copper is being
heating, cooling, and heat exchange. replaced by plastics for water pipes in both res-
While high-conductivity copper is required idential and commercial construction. In the
for electrotechnical and electronic uses, special area of corrosion-resistant materials, in addi-
copper qualities are chosen for other uses. About tion to plastics there are also stainless steel and
30 % of world copper production is used for al- titanium.
loying. Copper alloys are usually cold-worked; The movement toward making smaller and
only ca. 10 % of them are cast. smaller parts has been one of the most pervasive
Copper is frequently used in the chemical and and continuing pressures on the copper market.
food industries because of its high resistance to A dramatic drop in the use of copper has oc-
corrosion. There is substantial use of copper in curred in the widespread acceptance of printed
mechanical engineering, by fabricators of pre- circuits. The use of wire has plummeted. The
cision implements, in vehicle construction, and number and size of the connectors have dropped.
in ship building. There is increasing interest in On the other hand, miniaturization has steadily
copper building construction as a material for
Copper 57

decreased the cost of the final products, thus in- capita consumption of primary copper in the
creasing the number of units sold. United States has grown [195]:
At the same time, however, this drive towards
miniaturization, whether in the thickness of an Late twenties 7.5 kg
automotive radiator or in the size of an electronic Early thirties 2.5 kg
World War II 9.5 kg
component, is a challenge to the copper industry Postwar period 7.5 kg
to produce purer copper and more useful alloys 1970 13.3 kg
1979 14.6 kg
and to the copper fabricating industry to produce
the new miniaturized products.
In several applications copper is resisting During the 1980s, there has been no increase in
substitution by using new technologies. For ex- consumption in America and Europe and only a
ample in telecommunications, copper continues small increase worldwide. In the 1990s copper
to be the preferred signal carrier for the last mile. production increased due to industrial growth.
The new xDSL (Digital Subscriber Line) tech- Figure 36 shows the development of world
nology allows the existing copper infrastructure per capita consumption for 1950 to 1997.
of ordinary telephone wires to also carry high-
speed data. The installation of optical fiber in Cost of Copper Production and Copper
communication trunk lines has led to a revolu- Price. The cost of copper production is char-
tion in the telecom industry. Copper application acterized by high capital investment in mining
was partly displaced, but overall this increased projects and in smelters and refineries. Mining
the demand for copper. Another development is projects are financed by large consortiums and
the use of copper circuitry in silicon chip tech- banks. The capital investment for a green-fields
nology, which makes the microprocessors faster smelter is in the region of 2500 – 3000 $/t of
and lowers energy consumption. Another exam- design copper production. Smelter enlargement
ple is the automobile radiator, which was for- investment is approximately half that. There-
merly made of copper, which was then displaced fore, increased smelter production is preferably
by aluminum. New technology was developed achieved by enlargement.
for producing smaller and lighter copper brass In the last 15 years copper leaching projects
radiators with higher thermal conductivity than have been established. This is due to lower cap-
aluminum radiators. A final example for innova- ital investment than smelters (about half), and
tion in copper is the development of supercon- also leaching operations built to increases the
ducting power cables made from high-tempera- copper yield of ores.
ture superconductor wire. This technology will Operational costs are high due to energy con-
improve energy efficiency, and now projects in sumption, which is the most important factor.
Chicago and Tokyo have been started. 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-
8. Economic Aspects ing and beneficiation and the rest in smelting
and electrorefining. For secondary copper, com-
There are numerous tabular compilations of ing for example from copper scrap smelting and
statistics on copper resources, production, and refining, the overall energy consumption is only
consumption [192–196]. Many books deal with 20 GJ/t.
economic relations and commercial problems, Due to several smelter enlargements, leach-
e.g., [197–200]. Compilations of companies in ing operations, and also new energy-efficient
the nonferrous metal industry [201] and the min- milling and smelting/refining processes, the
ing industry [202] are published at irregular in- overall production cost of copper are falling.
tervals. The copper price is set primarily at the two
metal exchanges: the London Metal Exchange
Production and Consumption. The copper (LME) and the New York Commodity Exchange
production of mines, smelters, and refineries and (COMEX). Like the copper production cost also
the consumption by country and region are given the copper prices have been in an overall declin-
in Table 23. Over the decades, the annual per 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).
Copper 61

11. References 19. H. Y. Sohn, D. E. George, A. D. Zunkel (eds.):


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