Gold processing

WRITTEN BY:
• James Edward Hoffmann
See Article History

Gold processing, preparation of the ore for use in various products.

For thousands of years the word gold has connoted something of beauty or
value. These images are derived from two properties of gold, its colour and its
chemical stability. The colour of gold is due to the electronic structure of the
gold atom, which absorbs electromagnetic radiation with wavelengths less than
5600 angstroms but reflects wavelengths greater than 5600 angstroms—the
wavelength of yellow light. Gold’s chemical stability is based on the relative
instability of the compounds that it forms with oxygen and water—a
characteristic that allows gold to be refined from less noble metals by oxidizing
the other metals and then separating them from the molten gold as a dross.
However, gold is readily dissolved in a number of solvents, including oxidizing
solutions of hydrochloric acid and dilute solutions of sodium cyanide. Gold
readily dissolves in these solvents because of the formation of complex ions
that are very stable.
Gold (Au) melts at a temperature of 1,064° C (1,947° F). Its relatively high
density (19.3 grams per cubic centimetre) has made it amenable to recovery
by placer mining and gravity concentration techniques. With a face-centred
cubic crystal structure, it is characterized by a softness or malleability that lends
itself to being shaped into intricate structures without sophisticated
metalworking equipment. This in turn has led to its application, from earliest
times, to the fabrication of jewelry and decorative items.

History
The history of gold extends back at least 6,000 years, the earliest identifiable,
realistically dated finds having been made
in Egypt and Mesopotamia c. 4000 BC. The earliest major find was located on
the Bulgarian shores of the Black Sea near the present city of Varna. By
3000 BC gold rings were used as a method of payment. Until the time of Christ,
Egypt remained the centre of gold production. Gold was, however, also found
in India, Ireland, Gaul, and the Iberian Peninsula. With the exception of coinage,

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virtually all uses of the metal were decorative—e.g., for weapons, goblets,
jewelry, and statuary.
Egyptian wall reliefs from 2300 BC show gold in various stages of refining and
mechanical working. During these ancient times, gold was mined from alluvial
placers—that is, particles of elemental gold found in river sands. The gold was
concentrated by washing away the lighter river sands with water, leaving behind
the dense gold particles, which could then be further concentrated by melting.
By 2000 BC the process of purifying gold-silver alloys with salt to remove the
silver was developed. The mining of alluvial deposits and, later, lode or vein
deposits required crushing prior to gold extraction, and this consumed immense
amounts of manpower. By AD 100, up to 40,000 slaves were employed in gold
mining in Spain. The advent of Christianity somewhat tempered the demand for
gold until about the 10th century. The technique of amalgamation, alloying with
mercury to improve the recovery of gold, was discovered at about this time.
The colonization of South and Central America that began during the 16th
century resulted in the mining and refining of gold in the New World before its
transferal to Europe; however, the American mines were a greater source of
silver than gold. During the early to mid-18th century, large gold deposits were
discovered in Brazil and on the eastern slopes of the Ural Mountains in Russia.
Major alluvial deposits were found in Siberia in 1840, and gold was discovered
in California in 1848. The largest gold find in history is in the Witwatersrand
of South Africa. Discovered in 1886, it produced 25 percent of the world’s gold
by 1899 and 40 percent by 1985. The discovery of the Witwatersrand deposit
coincided with the discovery of the cyanidation process, which made it possible
to recover gold values that had escaped both gravity concentration and
amalgamation. With E.B. Miller’s process of refining impure gold with chlorine
gas (patented in Britain in 1867) and Emil Wohlwill’selectrorefining process
(introduced in Hamburg, Ger., in 1878), it became possible routinely to achieve
higher purities than had been allowed by fire refining.
Ores
The major ores of gold contain gold in its native form and are
both exogenetic (formed at the Earth’s surface) and endogenetic (formed within
the Earth). The best-known of the exogenetic ores is alluvial gold. Alluvial gold
refers to gold found in riverbeds, streambeds, and floodplains. It is invariably
elemental gold and usually made up of very fine particles. Alluvial gold deposits
are formed through the weathering actions of wind, rain, and temperature
change on rocks containing gold. They were the type most commonly mined in
antiquity. Exogenetic gold can also exist as oxidized ore bodies that have
formed under a process called secondary enrichment, in which other metallic

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elements and sulfides are gradually leached away, leaving behind gold and
insoluble oxide minerals as surface deposits.
Endogenetic gold ores include vein and lode deposits of elemental gold in
quartzite or mixtures of quartzite and various iron sulfide minerals, particularly
pyrite (FeS2) and pyrrhotite (Fe1-XS). When present in sulfide ore bodies, the
gold, although still elemental in form, is so finely disseminated that
concentration by methods such as those applied to alluvial gold is impossible.
Native gold is the most common mineral of gold, accounting for about 80
percent of the metal in the Earth’s crust. It occasionally is found as nuggets as
large as 12 millimetres (0.5 inch) in diameter, and on rare occasions nuggets of
native gold weighing up to 50 kilograms are found—the largest having weighed
92 kilograms. Native gold invariably contains about 0.1 to 4 percent
silver. Electrum is a gold-silver alloy containing 20 to 45 percent silver. It varies
from pale yellow to silver white in colour and is usually associated with
silver sulfide mineral deposits.
Gold also forms minerals with the element tellurium; the most common of these
are calaverite (AuTe2) and sylvanite (AuAgTe4). Other minerals of gold are
sufficiently rare as to have little economic significance.
Of the world’s known mineral reserves of gold ore, 50 percent is found in South
Africa, and most of the rest is divided among Russia, Canada, Australia, Brazil,
and the United States. The largest single gold ore body in the world is in the
Witwatersrand of South Africa.

Mining And Concentrating

The nature of the ore deposit determines the mining and mineral
processing techniques applied. Oxide ore deposits are frequently of such low
grade (e.g., 3 to 10 parts per million) that extensive mineral processing cannot
economically be justified. In this case they are merely shattered by explosives
and then piled into heaps for extraction by cyanidation (see below). These
heaps can be hundreds of metres long and 15 to 30 metres in height.
Alluvial deposits are either dredged from pond and river bottoms or sluiced from
banks and floodplains with high-pressure hydraulic hoses. Alluvial deposits
require little or no comminution; they are usually concentrated by gravity
techniques such as jigging or tabling, in which a slurry is passed through jigs or
over grooved or ridged tables that retain the denser gold particles while allowing
the much less dense sand and gravel to pass over.

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Endogenetic deposits frequently contain elemental gold that is highly
disseminated within a base metal sulfide mineral. These deposits are mined,
crushed and ground, and then concentrated first by gravity separation to
recover coarse particles of native gold before being subjected to froth flotationto
concentrate the sulfide mineral fraction that contains the gold.

Extraction And Refining

Amalgamation
Elemental gold (and silver as well) is soluble in mercury, so that, when particles
of the metal are brought into contact with a fresh mercury surface, they are
wetted and dissolved, forming an alloy called amalgam. This phenomenon is
exploited for the recovery and concentration of fine particulate gold or silver.
Amalgamation is accomplished by passing a slurry of ore over copper plates
coated with mercury, by mixing a slurry of ore and mercury in a cylindrical or
conical vessel called an amalgam barrel, or by grinding the ore in a ball, rod, or
pebble mill to free the gold from the mineral matrix and then adding mercury to
the mill and continuing grinding until the gold has dissolved in the mercury. The
denser amalgam is then separated from the now barren ore in the mill
discharge. After filtration and washing to remove impurities, the amalgam is
heated in a sealed retort to distill off the mercury, which is recovered for reuse.

Although amalgamation is still practiced extensively in gold recovery, the very

real hazards of mercury poisoning of either the operators or
the environment have limited its application and compelled the use of carefully
designed equipment to ensure against contamination.
Cyanidation
More gold is recovered by cyanidation than by any other process. In
cyanidation, metallic gold is oxidized and dissolved in an alkaline cyanide
solution. The oxidant employed is atmospheric oxygen, which, in the presence
of an aqueous solution of sodium cyanide, causes the dissolution of gold and
the formation of sodium cyanoaurite and sodium hydroxide, according to the
so-called Elsner reaction:

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When gold dissolution is complete, the gold-bearing solution is separated from
the solids.

With ores of higher gold content (i.e., greater than 20 grams of gold per ton of
ore), cyanidation is accomplished by vat leaching, which involves holding a
slurry of ore and solvent for several hours in large tanks equipped with agitators.
For extracting gold from low-grade ores, heap leaching is practiced. The huge
heaps described above are sprayed with a dilute solution of sodium cyanide,
and this percolates down through the piled ore, dissolving the gold.
Immense amounts of solution and solids are associated with a vat leaching
circuit, owing to the very low concentrations of gold in the ores. In order to
eliminate the huge capital costs associated with the purchase and installation
of solids/liquids separation equipment, techniques have been developed
that circumvent the entire separation process. One of these is the addition of
granular activated carbon to the ore slurry during or upon completion of gold
solubilization. The dissolved gold is readily adsorbed onto the carbon, thus
removing it from solution, and the granular carbon is separated from the now
barren ore by running the slurry through a screen. Gold is then leached from
the carbon particles by a strong solution of sodium cyanide and sodium
hydroxide, and it is recovered from solution by electrowinning directly onto steel
wool or by the Merrill-Crowe process. In the latter process, the gold-bearing
solution is deoxygenated and passed through a filter-press, where the gold is
displaced from solution by reduction with zinc metal powder.
Extraction from refractory ores
Many gold-bearing ores and concentrates are not readily amenable to
cyanidation, owing to the presence of substances that consume the cyanide
reagent before it can dissolve the gold, preferentially adsorb the gold as it
dissolves (a phenomenon called preg-robbing), or completely surround the gold
particles in such a way as to prevent access by the cyanide leach solution. Such
ores are referred to as refractory, and they frequently contain the sulfide
minerals pyrite, pyrrhotite, or arsenopyrite. Gold can be freed from these ores
or concentrates by treating them with various oxidizing processes. The most
common method is to roast gold-bearing minerals at temperatures of 450° to
750° C (840° to 1,380° F) to destroy the interfering sulfides. Oxidation can also
be accomplished by the use of high-pressure reactors called autoclaves, in
which the minerals in an aqueous slurry are treated at high temperature and
pressure with oxygen-bearing gases. After oxidation is complete, cyanidation,
as described above, is employed to solubilize and extract the gold.
A large proportion of gold is recovered from refractory ores, and considerable
skill is required in the design and operation of such facilities.

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Refining

Gold extracted by amalgamation or cyanidation contains a variety of impurities,

including zinc, copper, silver, and iron. Two methods are commonly employed
for purification: the Miller process and the Wohlwill process. The Miller process
is based on the fact that virtually all the impurities present in gold combine with
gaseous chlorine more readily than gold does at temperatures equal to or
greater than the melting point of gold. The impure gold is therefore melted and
gaseous chlorine is blown into the resulting liquid. The impurities form chloride
compounds that separate into a layer on the surface of the molten gold.
The Miller process is rapid and simple, but it produces gold of only about 99.5
percent purity. The Wohlwill process increases purity to about 99.99 percent
by electrolysis. In this process, a casting of impure gold is lowered into an
electrolyte solution of hydrochloric acid and gold chloride. Under the influence
of an electric current, the casting functions as a positively charged electrode, or
anode. The anode dissolves, and the impurities either pass into solution or
report to the bottom of the electrorefining tank as an insoluble slime. The gold
migrates under the influence of the electric fieldto a negatively charged
electrode called the cathode, where it is restored to a highly pure metallic state.
Although the Wohlwill process produces gold of high purity, it requires the
producer to keep on hand a substantial inventory of gold (mainly for the
electrolyte), and this is very costly. Processes based on direct chemical
purification and recovery from solution as elemental gold can greatly speed gold
processing and virtually eliminate expensive in-process inventories.

Refining from scrap

The processing of gold scrap varies not only with the gold content but also with
the amenability of the gold in the scrap to extraction. Thus, the bulk of the gold
may be recovered by leaching techniques using cyanidation or aqueous
chlorination, and the residue may then be treated by smelting to recover the
balance. Generally, scrap with a gold content of less than 0.1 percent, unless
readily recoverable by leaching, is recycled back to a pyrometallurgical process.
Metallic scrap gold from jewelry production is frequently melted on-site and
reused.

Assaying
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Fire assay is considered the most reliable method for accurately determining
the content of gold, silver, and platinum-group metals (except osmium and
ruthenium) in ores or concentrates. This process involves melting a gold-
bearing sample in a clay crucible with a mixture of fluxes (such as silica and
borax), lead oxide (called litharge), and a reducing agent (frequently flour). The
fluxes lower the melting point of the oxidic materials, allowing them to fuse, and
the molten litharge is reduced by the flour to extremely fine drops of lead
dispersed throughout the charge. The drops of lead dissolve the gold, silver,
and platinum-group metals, then coalesce and gradually descend through the
sample to form a metallic layer at the bottom of the crucible. After cooling, the
lead “button” is separated from the slag layer and heated under oxidizing
conditions to oxidize and eliminate the lead. The shiny metallic bead that is left
contains the precious metals. The bead is boiled in nitric acidto dissolve the
silver (a process called parting), and the gold residue is weighed. If platinum
metals are present, they will alter the appearance of the bead, and their
concentration can sometimes be determined by use of an arc spectrograph.
In the jewelry industry, gold content is specified by karat. Pure gold is
designated 24 karats; therefore, each karat is equal to 4.167 percent gold
content, so that, for example, 18 karats equals 18 × 4.167, or 75 percent gold.
“Fineness” refers to parts per thousand of gold in an alloy; e.g., three-nines fine
would correspond to gold of 99.9 percent purity.

The Metal And Its Alloys

Pure gold has virtually no industrial uses other than as a backing for currency.
In reality, no country backs its currency with an equivalent amount of gold, but
to some extent the solvency of a country is equated with its gold reserves.

Jewelry represents the single largest use of gold. Because of the metal’s
softness, it is alloyed with other metals to provide the requisite hardness and
strength. Typical jewelry alloys include gold-silver, gold-copper, and gold-silver-
copper. Most gold jewelry varies between 14 and 18 karats. Gold also finds
extensive use in the casting of dental bridges and crowns. Here it is usually
alloyed with silver and copper, although platinum or palladium are sometimes
added to increase strength.

Because of its combination of high electrical conductivity and high corrosion

resistance, gold is used in the plating of electronic contacts and transistor bases

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and in gold-based solders of extremely high reliability for semiconductor silicon
chips. Owing to its chemical stability, gold has virtually no applications as
a catalyst. However, it is sometimes used as a substrate for
platinum catalystsemployed in the production of nitric acid.

Chemical Compounds
Chemical compounds of gold include potassium dicyanoaurate, K[Au(CN)2],
used in gold electroplating baths, and chloroauric acid, HAuCl4, used as an
intermediate in the production of other gold compounds and occasionally for
colouring ceramics. Gold salts are also used as anti-inflammatory drugs in the
treatment of rheumatoid arthritis.
James Edward Hoffmann