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To a
large extent, copper
oxide
and sulfides are naturally
separated
in nature. As such, once mined the processing of the ore generally does
not need to separate the oxides and sulfides. Imagine this image as
Dixie Valley looking towards the Copper Mountain claim group.

Dissolved
copper from deep
underground cools to form the Primary orebody
Copper
orebodies are formed
when
geothermal
solutions bring copper dissolved from deep underground to cool near
surface environments where the copper and associated metals precipitate
as minerals in veins and disseminations within the rock. Copper is
usually deposited as copper sulfide minerals or in some environments as
native copper metal.
The most common copper minerals
in the primary hydrothermal zone are:
- Bornite
Cu5FeS4 Chalcopyrite
CuFeS2
Orebody
oxidization

Air or
water oxidizes some
of
the orebody
During
millions of years
the
mineral deposit may be exposed to
oxygen by air penetration, or by oxygen rich water flowing over it.
This oxidation alters the mineralogy, replacing the copper and iron
sulfides with carbonates and oxides as the sulfur is oxidized to
soluble sulfate and carried away in acid solution.
The iron
in the oxidized
zone
depends in part on the host rock
chemistry, but mostly under intensive oxidation the iron is oxidized
and stays as various hydrous iron oxides (goethite, limonite,
etc.) as the gossan or iron cap. In cases where
sulfates are left as alunite, jarosite
and so on the iron may move a bit more in solution. Abundant carbonate
would create a different environment.
The most common copper minerals in the
oxidized zone are:
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Atacamite Cu2Cl(OH)3
Azurite Cu3(CO3)2(OH)2
Cuprite
Cu2O
Chrysocolla CuSiO3(H2O)2
Malachite Cu2CO3(OH)2
NativeCopper Cu
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Secondary orebody enrichment

Water
enriches copper
below the
oxidized zone creating Secondary
enrichment zone (violet)
Beneath
the oxidized zone,
some
dissolved copper is
precipitated as secondary or supergene
copper minerals. This enriches the sulfides, making a secondary
enrichment, or transitional zone. The primary mineralization was caused
by the superheated geothermal solutions. The secondary enrichment
replaces iron in the minerals with more copper, further enriching the
ore.
The most common copper minerals in the
secondary
enrichment
zone are:
Chalcocite
Cu2S
Covellite CuS
Mines
In
prehistory, copper could
be
found as native copper on the
surface
of the ground. Prospecting for copper in this environment was
relatively simple. Over time, increased demand has meant that mining
has turned to more marginal forms of copper to continue supply. These
marginal copper sources are also much more difficult to locate. When a
copper body is discovered, drilling is undertaken to determine the size
of, and proportion of copper in (the grade), the orebody zones. If the
copper ore deposits is typical, it will be described in terms of the
number of tonnes (and the grade) of ore in each of the oxide, secondary
and primary zones. The tonnes and grade can be multipled together to
determine the amount of copper in the deposit, and the processing costs
for each zone can be used to determine mine profitability.
Currently
Chalcopyrite ore
is
extensively
mined in Chile,
the United States, Canada, Zambia, Kazakhstan, Mauritania and Poland.
In the United States, the states of Arizona, Montana, New Mexico, and
Utah lead in
ore mining. Indeed, the world's largest copper mine, the Chuquicamata,
is located in Atacama, Chile.
Most
copper currently is
mined
from large open
pit mines in porphyry copper deposits that
contain 0.4 to 1.0 percent copper. Examples include: Chuquicamata
in Chile
and El Chino mine in New
Mexico.
Reclamation and Regulation
The
requirements for
companies or
individuals to reclaim
copper
mines varies from country to country around the world. Regulations also
vary from state to state within the United States. For instance, the
State of New Mexico requires all hardrock mines to be reclaimed to a
self-sustaining ecosystem after mining has been completed. Financial
assurance is held by the state until the reclamation has been completed.
Hydrometallurgical Extraction
Oxide ores
Oxide
ores are readily
leached
by sulfuric acid, usually using a heap leach
or dump leach process in combination
with solvent extraction and electrowinning technology (SX-EW).
Commonly sulfuric acid is used as a leach for copper oxide, although it
is possible to use water. There have been examples where froth
flotation
was used to concentrate malachite.
In general froth flotation is not used to concentrate copper oxide
ores, as the cost of leaching is cheap when compared to the cost of
grinding and flotation. The implication of this is that
copper oxides are more economic to process than copper sulfides.
Secondary ores
Secondary
sulfides - those
formed
in secondary enrichment -
are resistant (refractory) to sulfuric leaching. High
grade secondary sulfides may be concentrated using froth flotation, and
subsequently smelted to recover the copper, or else they can
be leached using a bacterial oxidation
process to oxidize the sulfides to sulfuric acid, which also allows for
simultaneous leaching with sulfuric acid. As with oxide ores, solvent
extraction and electrowinning technologies are used to recover the
copper from the pregnant leach solution.
Pyrometallurgical Extraction
The
following is a process
of copper
extraction from
chalcopyrite ore into pure metal. While oxide ores can be processed
using Pyrometallurgical techniques, Hydrometallurgical methods are more
cost effective.
The
copper ore is crushed
and
ground before it is concentrated
to
between 20 and 40% copper in a flotation process. The next major step
in production uses pyrometallurgical processes to convert the copper
concentrate to 99% pure copper suitable for electrochemical
refining.
These high temperature processes first roast the concentrate, then
smelt it in a furnace, oxidise and reduce the molten products to
progressively remove sulfur, iron, silicon and oxygen to leave behind
relatively pure copper.
Concentration
All
copper sulfide ores are
concentrated using the froth flotation process. Ground ore is
mixed with xanthate reagents
(for example, pine oil), which reacts with the copper sulfide mineral
to make it hydrophobic on its surface.
The
sulfide ore is crushed
and
ground to increase the surface
area
of the ore for subsequent processing. The powdered ore is mixed with
pine oil (the 'collector chemical') and introduced to a water bath
(aeration tank) containing surfactant.
Air is constantly forced through the slurry and the hydrophobic mix of
copper and pine oil latches onto and rides the air bubbles to the
surface, where it forms a froth and is skimmed off. These skimmings are
cleaned of the collector chemical and surfactant , leaving copper
concentrate. The remainder is discarded as tailings,
or processed to extract other elements.
To
improve the process
efficiency, limestone
is used to raise the pH of the water bath, causing the collector to ionize
more and to preferentially bond to chalcopyrite
(CuFeS2)
and avoid the pyrite (FeS2) - iron exists in both
Primary zone minerals.
The
product from this froth flotation process is known as copper concentrate.
When the foam (which is between 20 and 40% copper) is dried it is known
as copper concentrate. Copper concentrate may be treated by either hydrometallurgical methods
or sintered
before pyrometallurgical
methods are used to produce copper metal. Copper concentrate is
sometimes traded either via spot contracts or under long term contracts
as an intermediate product in its own right.
Roasting
In the roaster, the copper concentrate
is partially
oxidised
to produce calcine and sulfur dioxide gas. The stoichiometry
of the reaction which takes place is:
2CuFeS2(s) + 3O2(g)
→ 2FeO(s)
+ 2CuS(s)
+ 2SO2(g)
Currently,
roasting is no
longer
common in
copper concentrate treatment. Direct smelting using the Flash Smelting or El Teniente furnace is now
used outside of the United States
Smelting
The
calcine is then mixed
with silica
and limestone
and smelted at 1200°C (in an exothermic
reaction) to form a liquid called matte. In copper recycling,
this is the point where scrap copper is introduced. Several reactions
occur. For example iron oxides and sulfides are converted to slag which
is floated off the matte. The reactions for this are:
FeO(s) + SiO2 (s)
→ FeO.SiO2
(l)
In a parallel reaction the iron
sulfide is converted to
slag:
2FeS(l) + 3O2 +
2SiO2 (l)
→
2FeO.SiO2(l) + 2SO2(g)
Conversion to Blister
The
matte, which is
produced in
the smelter, contains around
70%
copper primarily as copper sulfide as well as iron sulfide. The sulfur
is removed at high temperature as sulfur dioxide by blowing air through
molten matte:
CuS(l) + O2(g) →
Cu(l)
+ SO2(g)
In a parallel reaction the iron
sulfide is converted to
slag:
2FeS(l) + 3O2 +
2SiO2 (l)
→
2FeO.SiO2(l) + 2SO2(g)
The end
product is (about)
98%
pure copper known as blister
because of the broken surface created by the escape of sulfur dioxide
gas as the copper ingots are cast. By-products generated in the process
are sulfur dioxide and slag.
Reduction
The
blistered copper is put
into
an anode furnace (a furnace that
makes anodes)
to get rid of most of the remaining oxygen. This is done by blowing natural
gas
through the molten copper oxide. When this flame burns green,
indicating the copper oxidation spectrum, the oxygen has mostly been
burned off. This creates copper at about 99% pure. The anodes produced
from this are fed to the electrorefinery.
Electorefining
The
copper is then put into
sheets which are refined by electrolysis.
The copper anodes are placed into a solution of copper sulfate and
sulfuric acid. The copper then migrates across the solution to the
cathode, also made of copper to maintain purity. The reactions are:
At the anode: Cu(s)
→ Cu2+(aq)
+ 2e-
At the cathode:
Cu2+(aq) + 2e-
→ Cu(s)
A copper
cathode is 99.97%
copper
in sheets of dimensions: 96 cm x 95 cm x 1 cm, with a mass of about 100
kg. It is a true commodity, deliverable to the metal exchanges in
New
York, London
and Shanghai.
The chemical specification for electrolytic
grade copper is ASTM B 115-00.


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