EXTRACTIVE METALLURGY OF GOLD

6. Recovery from solution

Fathi Habashi
Laval University, Quebec City, Canada
Fathi.Habashi@arul.ulaval.ca

Refining is a necessary step in treating a metal

to decrease its impurities so that it can be used
for a variety of purposes.
Physical and electrochemical properties of a
metal are greatly influenced by the level of
impurities. Thus ductility, electrical
conductivity, and other properties improve
remarkably with increased purity.
Refining is, therefore, an important
metallurgical operation.

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 New techniques have to be developed for
producing pure metals and new methods
of analysis have been devised for quality
control.
Raw gold ingots produced at the mine site
or scrap gold are shipped to refiners for
obtaining pure ingots by pyro- , hydro- , or
electrometallurgical methods.
Silver refining is almost always associated
with a gold refinery.
Fire assay is still widely used for gold
determination in raw ingots.

PYROMETALLURGICAL
REFINING
Refining of gold bullion by selective oxidation using
chlorine gas is known as the Miller Process after its
inventor Francis B. Miller (1828-
(1828-1887), and is used at
some mints.
In this process the bullion is melted, then poured into
heated clay crucibles containing borax, which forms a
molten layer on the surface of the bullion.
The crucibles, about 20 cm in diameter and 30 cm high,
are heated in a furnace.
Each crucible is provided with a slotted cover to allow
inserting or withdrawing of clay pipes through which
chlorine is admitted.
As a safeguard against leakage or breakage, each
crucible is placed inside a graphite crucible.

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 The base metals are attacked first and volatilize
as chlorides.
They are collected in a flue dust recovery system.
After the base metals have been practically
eliminated, silver is attacked next and AgCl (m.p.
455C) floats on the surface of the gold beneath
the borax layer.
It is skimmed off and collected for silver
recovery.
Chlorination is complete and the gold is ready for
casting when a clay rod held in the fumes forms
a brownish stain indicating the formation of gold
chloride.

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 HYDROMETALLURGICAL REFINING

Small scale refining of gold, e.g., in mints, is

done by selective leaching.
The method used depends on the gold content as
well as on the type of impurities present.
While silver is soluble in both nitric and sulfuric
acids, and gold is insoluble, yet these acids
cannot be used to dissolve silver away from an
alloy containing more than 25% Au.
For high-gold alloys, aqua regia is therefore used.
In such alloys, gold is leached, while silver forms
an insoluble residue.

Gold is soluble in aqua regia, but a goldsilver

alloy containing more than 8% Ag cannot be
attacked due to the formation of an insoluble
layer of AgCl.
Therefore, the aqua regia leaching process is
used only for refining high-grade bullions, where
the silver does not amount to more than 8%, or
to cases where the bullion contains enough
copper to open it up to attack in spite of the
silver present.
In both cases, the bullion is first melted and
poured in water to obtain granules suitable for
leaching.

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 = attacked,
attacked, x = not attacked

Alloy
composition Attack by
Alloy [%] Remarks
HNO3 or Aqua
Ag Au
H2SO41 regia2
Low-gold 100 0 x Bullion treated by HNO3 or H2SO4.
bullion 75 25 x
70 30 x x Bullion must be alloyed with Ag before treatment
50 50 x x with HNO3 or H2SO4.
25 75 x x
10 90 x x
High-gold 8 92 x Bullion treated by aqua regia.
bullion 0 100 x

Low-gold alloys

In such alloys, silver is selectively leached. It

is necessary to alloy the bullion with silver
such that silver constitutes 75% of the alloy.
Such an alloy is known as parting alloy.
In the nitric acid process the reactions are:
3Ag + 4HNO3 3AgNO3 + 2H2O + NO
3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO

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 HNO3 AuAg parting alloy

Leaching
Water

Drying
Filtration Washing melting Gold
Au casting
residue
NaCl

Precipitation
of AgCl

Fe

Cementation

Silver

The reaction is carried out in stainless steel vessels, and

nitric gases are oxidized and recovered as HNO3.
Silver and platinum will go into solution, while Au, Ru, Rh,
and Ir are left behind as a finely divided black mud.
Silver is recovered from the solution by precipitation as
AgCl by adding NaCl.
Silver chloride is then converted to metallic silver by
contact with scrap iron.
The gold residue is then washed, dried, melted, and cast

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 The introduction of sulfuric acid as a leaching agent
for refining gold reduced the cost greatly as compared
with the nitric acid process.
Cast iron vessels could be used, and copper in the
bullion is converted to copper sulfate, which is a
marketable product.
The process is shown in Figure 3 and the reactions
are:
2Ag + 2H2SO4 Ag2SO4 + 2H2O + SO2
Cu + 2H2SO4 CuSO4 + 2H2O + SO2

H2SO4 AuAg parting alloy

Leaching
Water
Solids
Drying Gold
Siphoning Washing melting
casting
Solution to waste
Crystallization
Fe
Solids
Filtration Silver
Ag2SO4

Crystallization

Filtration CuSO4 5H2O

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 Silver, copper, and part of the palladium are dissolved, while Au, Pt, Ru, Rh,
and Ir are not.
The gold residue is separated, washed, dried, briquetted, melted, and cast.
The solution containing silver and copper is transferred to lead-lined tanks,
diluted with water, and cooled to crystallize Ag2SO4.
Silver sulfate is slightly soluble in cold water but dissolves readily in hot
concentrated H2SO4.
The crystals are separated, washed, reduced with scrap iron, melted, and cast.
The mother liquor is evaporated and cooled to crystallize and separate CuSO4.
The residual sulfuric acid is recycled. This process cannot be used for bullions
containing appreciable quantities of lead, because PbSO4 will be left behind
with the gold residue and considerable fluxing of the final product would be
necessary to remove it.

High-gold alloys

Aqua regia is used to attack high-gold alloys since

both nitric and sulfuric acids are not effective.
In this method, gold, copper, and other impurities go
into solution while silver remains behind as silver
chloride. The leaching equations are:
2Au + 3Cl2 2AuCl3 (soluble)
2Ag + Cl2 2AgCl (insoluble)
Cu + Cl2 CuCl2 (soluble)

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 The dissolving pans are made of stoneware, glass, or
fused silica and have a capacity of about 250 liters.
Each pan is filled two-thirds with HCl and heated by
steam injection. The nitric acid is added at intervals to
maintain a vigorous reaction.
The dissolution of gold follows the equation:
4HCl + HNO3 + Au HAuCl4 + NO + 2H2O
When the process is complete, the excess acid is
boiled off:
HNO3 + 3HCl NOCl + 2H2O + Cl2

The liquor is allowed to settle, and the

supernatant solution is siphoned and treated
with a reducing agent (e.g., FeCl2, oxalic acid,
SO2) to precipitate gold, which is filtered off,
washed, and melted.
Silver chloride residues are washed with water,
and the first washings (containing gold) are
returned to the dissolving pan. The material is
then reduced with scrap iron to metallic silver.

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 Aqua regia
AuAg bullion
(Ag < 8%)

Leaching

Boiling Water Fe

Solids Silver
Settling Washing Cementation
AgCl

Reduction
Water
Drying Gold
Filtration Washing melting
casting

Solution
to waste

This process is of special value when

refining platiniferous gold.
Platinum and palladium are dissolved
together with gold, while Rh, Ru, and
Ir remain with the silver chloride.
Gold is precipitated by FeCl2, and
then filtered, and Pt and Pd are
recovered from the solution by the
usual methods.

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 Solvent extraction of gold

Gold can be extracted from chloride

solutions by a number of organic
solvents. For example:

The Harmony Refinery

A sludge containing between 50 and 85% gold
was solubilized by leaching for 2 hours in
hydrochloric acid under chlorine gas stream.
The bulk of the base metals and platinum group
metals are also solubilized under these
conditions.
Silver precipitates as silver chloride and is
collected as a solid residue along with any silica.
This material can be treated in a separate
processing step to recover residual gold and
purify the silver.

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 The leach solution, containing about 65 g/L gold, is
treated by solvent extraction [the organic solvent
was not specified].
Gold is selectively extracted into the organic phase,
while all other metal ions report to the rafinate.
Small quantities of co-extracted impurities are
scrubbed from the loaded organic phase before it is
stripped to produce a purified, concentrated gold
solution.
The stripped organic phase is then recycled to the
extraction circuit. The HCI-rich rafinate from the
extraction section is returned to the leach, with a
small bleed to control the build up of base-metal
impurities in the leach/solvent extraction circuit.

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 Gold is recovered as a metal powder by
direct reduction from the loaded strip
liquor.
Use of gaseous sulfur dioxide as the
reducing agent produces gold meeting the
specification of 99.99% purity.
The leach and reduction are operated
batchwise, while the solvent extraction is
a continuous operation.
Equipment is mainly made of fiber-
reinforced plastic, polypropylene, and
high-density polyethylene.

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 ELECTROMETALLURGICAL
REFINING

In electrorefining technology the impure metal is cast in form of anode,

then dissolved electrolytically:
M Mn+ + ne
The metal ion liberated at the anode migrates towards the cathode and
deposits on its surface.
The anodes cannot be dissolved completely, and between 10% and
30% of its weight remains at the end of the cycle as anode scrap.
The scrap is recycled. When soluble impurities can co-deposit onto the
cathode together with the metal to be refined, then the cathodes are
placed in diaphragm-equipped boxes.
The impure anolyte is withdrawn from the common anode
compartment, purified and returned to the cathode boxes.
Energy consumption is low because the anodic reaction is the same as
the cathodic.

The electrometallurgical route is conducted in

Wohlwill cell named after its German inventor Emil
Wohlwill.
Feed material is usually the anode slimes from silver
refining. These are collected, purified to remove
silver, and cast as anodes containing approximately
94% Au, 5% Ag, and 1% Cu, Pt, Pb, and Pd and
measuring about 20 x 10 x 1 cm.
Electrolysis is carried out in acidic chloride solutions
containing 150200 g/L Au and 140 g/L HCl at about
70C and at a current density of 1 200 A/m2, using
thin gold ribbon cathodes.

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 At the anode, the reaction
Au + 4Cl [AuCl4] + 3e
takes place, and at the cathode the reverse
reaction. Anodes and cathodes are normally
replaced every two days.
During electrolysis impurities go into solution,
silver precipitates as silver chloride, and pure
gold deposits on the cathode.
These are lifted out of the solution periodically to
remove the nodules and thereby prevent short-
circuiting between cathode and anode.
Electrolyte is replaced periodically when the total
concentration of platinum and palladium in the
electrolyte exceeds about 75 g/L.

Some gold is present in the silver chloride slimes due to the

disproportionation of monovalent gold in solution:
3Au+ 2Au + Au3+
The electrolyte from the gold refining process contains Pt, Pd, etc.
These metals are recovered by precipitation as (NH4)2PtCl6 and
(NH4)2PdCl6 then decomposition to sponge metal.
High-purity gold 99.999% is obtained by melting and casting the
cathodes in form of anodes and repeating the process.
The advantage of the process is the high purity of the gold produced
usually 99.9%. In addition, the by-products, especially platinum-group
metals, are also relatively easy to isolate.
A disadvantage is the fairly long period during which the noble metal
is tied up, leading to considerable financial losses.

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 Silver

Silver is usually the major impurity in gold and most gold refineries have a
silver refining unit.
Electrolysis is carried out in silver nitratesodium nitratenitric acid
electrolyte containing 150 g/L Ag (pH 11.5) at a current density of 300 A/m2
and a temperature of 35C.
Pure silver deposits on the cathode while gold and platinum remain insoluble
and are collected in the slimes. Copper, lead, and palladium accumulate in
solution.
When the copper or lead content in the electrolyte exceeds 10 g/L, or the
palladium content exceeds 1 g/L, the solution is removed, de-silverized, and
discarded, and new electrolyte is made by dissolving scrap anodes in hot nitric
acid.
Silver deposited in a loose crystalline form is collected, melted, and cast as
1 000-oz bars of 99.99% purity.
Higher purity of 99.999% is obtained by double electrolysis.
Electrolysis is usually conducted for two days and the residual anodes are 5 to
5% of the original.

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 ThumBalbach cell

These cells are mainly used in North America. They

consist of shallow tanks equipped with graphite or
stainless steel bottoms acting as cathodes.
The anodes are arranged horizontally above the
cathodes, resting on wooden frames with canvas
bags to retain the slimes.
Each cell is provided with only one anode and one
cathode. The cathode is a stainless steel plate
covering the entire floor area. Above this, at a
distance of 10 cm, is a slightly smaller framework of
nonconducting material, covered with fabric and
containing the anode.
The crude silver anodes are completely covered by
electrolyte. An advantage of this cell is that the
anode slime is recovered easily. Disadvantages
include the large space requirement and high energy
consumption.

Anode basket
Anode bag

Silver anodes
Electrolyte

Ano dic slimes

Silver crystals

Cathode

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 Moebius cell

These cells are mainly used in Europe. In these

cells the anodes and the stainless steel cathodes
are arranged vertically.
Each anode is encased in a polypropylene or
canvas bag which collects the slimes. Electrolyte
mixing is accomplished by an oscillating cathode
scraper which also brushes the silver crystals off
the cathode plates.
The crystals are collected in a removable basket
with a filter cloth bottom, which is situated
beneath the electrode.
The cell voltage is 2.02.5 V and the energy
consumption is about 0.6 kWh/kg of silver.

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 Silver anodes
+ +

Cathodes

Electrolyte
Me chanical
scraper

Anode bag

Silver crystals

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 The spent anodes are replaced continually by new
anodes, so that interruption of electrolysis is
necessary only if the electrolyte must be replaced
due to excessive copper concentration, or if the
anode bags have to be emptied. The electrolyte is
usually treated with copper to recover the silver by
cementation, and the copper is then recovered by
cementation with iron.
The process is most suitable for crude silver
containing > 90% Ag. With high copper content, the
electrolyte must be regenerated too often, and with
high gold content, the anode bags require frequent
emptying. Both are costly operations. A single
electrolysis gives a purity of 99.9599.99% Ag and a
double electrolysis gives a purity of 99.995
99.999%.

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