EXTRACTION OF GOLD

A Term paper on Extraction of Gold

Supervised by Dr. Ajay Kumar Shukla

Group Members:

1. MM19B006 Anand Selestine

2. MM19B050 Saka Manoj Kumar
3. MM19B010 Koduri Mohan
4. MM19B037 Madugula Padma
5. MM18B025 Omendar Mina

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We sincerely thank Dr. Ajay Kumar Shukla for giving us the opportunity to

take up this project as part of the course MM2080: Principles of Extractive

Metallurgy.

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Introduction
For thousands of years the word gold has connoted something of beauty or value. Gold is one
of the densest of all metals. It is a good conductor of heat and electricity. It is also soft and
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. 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

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 elements and sulfides are
gradually leached away, leaving behind gold and insoluble oxide minerals as surface
deposits.
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Endogenetic gold ores include vein and lode deposits of elemental gold in quartzite or
mixtures of quartzite and various iron sulfide minerals, particularly pyrite (FeS 2) 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 millimeters (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 color and is usually associated with silver sulfide mineral
deposits.

Mining and concentrating

The nature of the ore deposit figures out the mining and mineral processing techniques
applied. Oxide ore deposits are often 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 meters long and 15 to 30 meters in height.

Endogenetic deposits often have elemental gold that is highly given within a base metal
Sulphide 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 flotation to concentrate the Sulphide mineral fraction that has the gold.

The process of removal of the gangue from Ore is known as Concentration or Dressing or
Benefaction. There are many methods of concentration and the methods are chosen based
on the properties of the ore.

Hydraulic Washing:

This method concentrates the ore by passing it through an upward stream of water whereby
all the lighter particles of gangue are separated from the heavier metal ore. This is a type of
gravity separation.

Magnetic Separation:

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This involves the use of magnetic properties of either the ore or the gangue to separate them.
The ore is first ground to fine pieces and then passed on a conveyor belt passing over a
magnetic roller. The magnetic ore stays on the belt and the gangue falls off the belt.

Froth Flotation Method:

This method is mainly used to remove gangue from sulphide ores. The ore is powdered and
a suspension is created in water. To this are added, Collectors and Froth Stabilizers.
Collectors (pine oils, fatty acids etc.) increase the non-wettability of the metal part of the ore
and allows it to form a froth. Froth Stabilizers (cresols, aniline etc.) sustain the froth. The oil
wets the metal and the water wets the gangue. Paddles and air constantly stir up the
suspension to create the froth. This frothy metal is skimmed off the top and dried, to recover
the metal.

Leaching:

Leaching is used when the ore is soluble in a solvent. The powdered ore is dissolved in a
chemical, usually a strong solution of NaOH. The chemical solution dissolves the metal in the
ore and it can be extracted and separated from the gangue by extracting the chemical
solution. Extraction of the Aluminum metal from Bauxite ore is done using this process.

Gold extraction and processes related

The most efficient gold extraction processing route is related to the inherent mineralogical
features of the gold ore being processed.

The mineral assemblage decides the performance of all chemical and physical processes
involved in gold extraction

(e.g., Chryssoulis and Cabir, 1990; Marsden and House, 1992; Chrysoula's and McMullen,
2005).

It is therefore crucial to accurately characterize the mineralogical nature of the ore to be

processed; i.e., characterization of the precious metal phases (gold deportment) and gangue
minerals.

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 • Therefore, A wide range of metallurgical techniques are used to test the
extractability of gold from gold ore. The most common metallurgical tests employed
are: -
1. direct cyanidation
2. gravity separation
3. diagnostic leaching.

Methodology of extraction

The Mineralogical characterization and gold deportment studies must be done on

representative samples of the different or variable domains or zones within the ore body.

Usually, a full gold deportment study includes:

• Crushing and milling to achieve the required particle size distribution.

• Head chemical analysis and gold assays.
• Modal mineralogy.
• Grading analysis.
• Heavy liquid separation analysis.
• Gravity separation analysis.
• Gold deportment of particulate gold in the head sample and/or gravity concentrate
and/or heavy liquid separation (HLS) sinks fraction.
• Direct cyanidation of the head sample.
• Diagnostic leach analysis of the head sample and/or gravity tailings.

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F.1-Gold deportment test work options are illustrated in Fig. A full gold deportment study may not always be done on the
head material, due to grade, time and cost constraints.

• Crushing and milling- Most gold ores should be milled to at least 50–80% passing
75 µm for effective gold exposure (Marsden and House, 1992). Therefore, at least 10
kg of each representative composite sample is milled to 50% passing 75 µm for the
initial test work (grading, heavy liquid separation and/or gravity separation). A split
aliquot of 1 kg is milled to 80% passing 75 µm for head chemical analyses (including
gold assays), mineralogical characterization, gold deportment and cyanidation test
work. If it is known that the ore has very fine-grained gold, then finer grinding down
to 80% passing 53 µm may be needed.

Below diagram shows the cumulative grain size distribution of gold after crushing and milling -

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 • Head Assays and Chemistry- In this, Splitting the aliquots of each composite sample
(50% passing 75 µm) are analyzed by X-ray Fluorescence (XRF) for major elements.
The arsenic and silver grades are decided by Atomic Absorption Spectroscopy
(AAS). Multiple gold analyses are done by fire assay AAS finish (30 g split aliquots).
• Grading Analysis-The grading analysis gives a sign of the gold grain association with
predominantly coarse-grained or fine-grained particles. If a substantial proportion of
the gold reports to the coarse fractions, then there is a strong possibility that the ore
has coarse gold.
• Heavy Liquid Separation-Gold may be upgraded by heavy liquid separation (HLS).
HLS analysis is conducted on a 500 g to 1 kg sub-sample (050% passing 75 µm),
deslimed at 25 µm, using TBE @ 2.96 SG.

The result of the HLS gives an indication of the amenability of the ore to gravity recovery.
However, since the sample must be de-slimed for HLS to be effective.

The below diagram shows the results of heavy liquid separation analysis-

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 • Gravity Concentration- It is the separation of gold from other minerals based on
density.
• Mineralogical Composition-X-ray Diffraction (XRD), optical microscopy and
QEMSCAN Bulk Modal Analysis (BMA) are employed to obtain the detailed
quantitative mineralogical composition of each sample.
• XRD analysis is done to find the major minerals present. Data collection is done using
an X-ray diffractometer employing Co-radiation, since most gold ores are iron-rich
and this causes X-ray fluorescence (resulting in a high background) when Cu-
radiation is used.
• QEMSCAN BMA is done on two 90 cut polished sections, designed to limit bias related
to the settling of heavy or large particles. The detection limit of BMA analysis can be
as low as 0.01%,
• Optical microscopy is employed to find carbonaceous components (e.g., kerogen) not
easily found by XRD or BMA.

Methods
GOLD CYANIDATION (also known as the cyanide process or the MacArthur-Forrest process): -
- It is a hydrometallurgical technique for extracting gold from low-grade ore by
converting the gold to a water-soluble coordination complex. It is the most used leaching process
for gold extraction.

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 • In this process the ore is comminuted using grinding machinery. Depending on the
ore, it is sometimes further concentrated by froth flotation or by centrifugal
(gravity) concentration. Water is added to produce a slurry or pulp. The basic ore
slurry can be combined with a solution of sodium cyanide or potassium cyanide;
many operations uses calcium cyanide, which is more cost effective.
• To prevent the creation of toxic hydrogen cyanide during processing, slaked lime
(calcium hydroxide) or soda (sodium hydroxide) is added to the extracting solution
to ensure that the acidity during cyanidation is kept over pH 10.5 - strongly basic.
Lead nitrate can improve gold leaching speed and quantity recovered, particularly
in processing partially oxidized ores.
• In some ores, particularly those that are partially sulfurized, aeration (prior to the
introduction of cyanide) of the ore in water at high pH can make elements such as
iron and sulfur less reactive to cyanide, therefore making the gold cyanidation
process more efficient. Specifically, the oxidation of iron to iron (III) oxide and
subsequent precipitation as iron hydroxide minimizes loss of cyanide from the
formation of ferrous cyanide complexes. The oxidation of sulfur compounds to
sulfate ions avoids the consumption of cyanide to thiocyanate (SCN−) byproduct.

Chemical reaction included - EISNER

EQUATION

4 Au(s) + 8 NaCN(aq) + O2(g) + 2H2O(l)→ 4 Na [Au (CN)2] (aq) + 4 NaOH(aq)

In this redox process, oxygen removes, via a two-step reaction, one electron from each gold
atom to form the complex Au (CN)−2 ion.

• In this process Oxygen is one of the reagents consumed during cyanidation, accepting
the electrons from the gold, and a deficiency in dissolved oxygen slows the leaching
rate. Air or pure oxygen gas can be purged through the pulp to maximize the dissolved
oxygen concentration.
• Due to high toxicity of cyanide other extractants like thiosulfate (S 2O32−), thiourea
(SC(NH2)2), iodine/iodide, ammonia, liquid mercury, and alpha-cyclodextrin are
used.
4. Gravity Separation Method - Gold gravity separation refers to the gold extraction and
separation process making use of different moving speed and direction of mineral
with different particle sizes, traits and proportion under the joint action of gravity,
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 centrifugal force, medium resistance and mechanical resistance. It is the oldest gold
extraction method.

Gold generally occurs in a form of monomeric native gold in alluvial gold mines, and the
particle size is generally greater than 16g/t. Therefore, gold gravity separation is one of the
most effective and economical processing methods for alluvial gold extraction

Types: -

• Jiggling gold gravity separation

• Shaking table gold gravity separation
• Spiral chute gold gravity separation
• Cone concentration gold gravity separation

Cons-

• using the gravity separation process to extract gold, the recovery rate of gold would
be low. This process needs to be combined with flotation, cyanidation and other
processes.

Pros-
• Straightforward process and low investment
• No need to use chemicals, low mineral processing cost, less pollution to the
environment.
• In some cases, using gravity separation to pre-concentrate, and using flotation or
cyanidation to extract the middling can save the cost.
• Suitable for the extraction of coarse gold.

REFINING

 This refers to processes used to process used to extract and separate the precious
metals in mined material, doré, and from recycled products (jewelry and electronics).
 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.

1.MILLER PROCESS

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 2.WOHLWILL PROCESS

MILLER PROCESS

In order to purify gold and remove the silver from it by any process analogous to the
cementation with nitre or salt in a reasonable time, the alloy must be in such a fine state of
division that the silver will be removed almost instantly, or diffusion must be assisted by
actually keeping the alloy in a molten state. Nitric acid, the active ingredient in the first
cementation process described, would not be effective in this case, since even if nitrate of
silver did form, the temperature is so high that it would be decomposed into oxide of silver,
and finally metallic silver and oxides of nitrogen. In fact, nitric acid itself would not be stable
at this temperature

The second active agent was chlorine, or hydrochloric acid, and as the former is known to be
much more active than the latter, a process of refining by this means was devised by Mr.
Lewis Thompson in 1838. The alloy was melted in a vessel and a stream of chlorine allowed
to pass over it. The silver was rapidly converted into chloride, and the gold was thus
rendered pure. Later experimentalists found that there was no volatilisation of gold in this
process, and that the addition of a chloride of the alkalies or alkaline earths prevented the
volatilisation of the chloride of silver formed. It is somewhat difficult to believe that no gold
volatilises during such an operation, for if pure gold is heated in a current of chlorine, yellow
feathery scales of the chloride will sublime on the upper part of the tube some distance from
the flame. This volatilisation is not appreciable until the silver has been removed.

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 The Miller process is an industrial-scale chemical procedure used to refine gold to a high
degree of purity (99.5%). It was invented by Francis Bowyer Miller (patented 1867). doré
bar is a semi-pure alloy of gold and silver. It is usually created at the site of a mine and then
transported to a refinery for further purification.

In the Miller process the ore bar is melted in induction furnace where the chlorine gas is
introduced into the molten metal by a rotating lance. The lance is controlled in a very precise
manner in a way there is no breakthrough of the chlorine gas to the surface of the molten
metal. This removes what are termed “By-metals” like silver, copper, nickel along with any
other metals. The process also removes amphoteric elements like sulfur, selenium,
tellurium, arsenic, and bismuth. These elements are all removed from the molten metal as
chloride slag that floats to the surface of the charge where they are skimmed off for further
treatment.

The process takes from 2 to 4 hours to complete with the chloride fumes being removed and
filtered by a two-stage wet filter or a two-stage dry scrubbing system that maximizes the

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recovery of the chloride as well as the cleaning of the exhaust air from the process. In the
process slag is poured off the top of the melt into a crucible and allowed to slowly cool so any
gold that has been caught up with the chlorides will settle to the bottom where it can be
recovered as a button of gold when the crucible has cooled completely; it is then added to
the remaining molten gold. In this process the particles of gold remaining in the crucible are
carefully removed by hand as well as the separation molds when they are cooled.

Once the gold has cooled it is poured through a ceramic filter directly into the granulation
equipment or anode molds if the Wohlwill process is used to further refine the gold.

The Crucibles and Connections

The pot in which the gold is melted prior to passing chlorine through is made of clay of fine
texture, similar to French clay. These are 10½ inches high, 5 inches in diameter, 3/8 of an
inch thick at the top, and gradually increasing to 1 inch at the bottom. These pots are fitted
loosely into a guard pot for safety; the guard pot is a plumbago crucible, 8¼ inches high, 6
inches internal diameter, 5/8 inch thick at the top, and ¾ of an inch thick at the bottom. This
stands in a cylindrical fire brick 5 inches in diameter, and 2½ inches high. Fire-clay lids,
dished to catch any gold projected by too rapid a current of gas, and having a slit in them to
allow of sliding them over the pot without shifting the chlorine pipe are provided.

The, pipe stem is 24 inches long, tapering from 3/8 to ½ an inch at the end inserted into the
gold, and is wedge-shaped to facilitate the escape of the chlorine when resting on the bottom
of the pot. The bore is 1/8 inch in diameter. The thin edge of the pipe stem is attached to the
branch delivery pipe by a piece of ½ inch rubber, about 2½ inches long, which connects with
an ebonite junction, G, 3 inches in length, with a bore of 1-10 inch, turned with a ring round
the middle, which acts as a rest for the 8oz. weight, H, used as a sinker for the pipe stem. One
end of the ebonite junction is ½ inch in diameter, the other ¾ inch, the latter being connected
by a stout rubber tube 3 or 4 inches long, to a 14-inch lead pipe, ½ an inch in diameter, which
is connected by a rubber junction to a glass stopcock, I, from the spigot of which a ¾lb. lead
weight, J, is suspended to prevent the pressure of gas from blowing it out.

The Chlorine Generators

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The jar generators described by Dr. Rose have been thrown out, and two Edwards’ Patent
Chlorine Generators installed.
These consist of semi-cylindrical vessels hung on trunnions.

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The vessel is made of boiler plates riveted together, and lined with sheet lead. The lead is
corrugated below so as to give greater strength, but is smooth inside, steam is admitted
through a pressure regulator through a trunnion on one side, and fills the space between the
lead and iron, thereby providing a steam jacket, the pressure, and therefore the temperature
of which is controlled by the regulator; any condensed steam is drained off by means of a pet
cock provided; steam escapes through a pipe leading through the other trunnion.

One comer of the generator is attached by means of a connecting rod to a crank which gives
it an oscillating motion, thereby preventing the chemicals from packing or becoming baked
on the hot lead surface. Holes about 6 inches in diameter left in the flat cover of the generator.
These serve for the introduction of the manganese dioxide and acid, and also for washing out
the salts. After the charge is exhausted, lead¬faced, flat iron covers are removed: these are
readily fastened in position by the pressure of a screw bolt at their centre. The screw passes
through a horizontal bar, the ends of which slip under projecting lugs riveted on to the
generator. The acid is supplied through a siphon pipe near the centre of the flat surface of

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the generator; the longer limb being sufficient to prevent the acid being thrown out by the
internal pressure of the gas.

The chlorine escape pipe passes through the cover, and is connected with a fixed leaden pipe
at a point opposite one of the trunnions, so that the oscillation of the generator will only give
a minimum movement at this point.

The charge used consists of 100lb. manganese dioxide 130lb. salt 275lb. sulphuric acid.

The two generators are used alternately, except when it is required to refine a large amount
of gold; in such a case the two generators are used together. When the charge is exhausted
in one generator it is connected to the second, and the chlorine gas still remaining is
displaced by gradually filling the vessel with water. One of the cover plates is then removed,
and the charge is emptied into an underground drain.

The gas passes through a pair of earthenware jars provided with two necks, in which many
of the acids or salts mechanically carried over are retained. From these the gas delivery pipe
leads to a distributing vessel with two necks, and partly filled with manganese chloride
solution. A pressure gauge of 1 inch glass tube 15 feet high is luted to the bottom of this
vessel, and fixed to the wall by brackets. Since one inch of gold will balance a column of about
19 inches of water, the liquid in this tube must be from 10 to 11 feet in height to force chlorine
through the 7 inches of gold in the pots. The pressure exerted is about 5lb. per square inch.
A four-way tube of lead or pottery is pressed through the second neck of the vessel, and each
arm is connected by thick rubber to glass stopcocks to which ½ inch lead pipes are joined,
these pipes leading to sets of four and five furnaces.

When the flow of chlorine through the gold is stopped the chlorine escapes through a safety
pipe. This is provided by having a two-necked earthenware vessel containing such a quantity
of water that when the pressure of the gas exceeds the working pressure required, the end
of a glass tube, passing to the bottom of the vessel, and connected above the neck with 4-inch
lead pipe ten feet high, becomes unsealed, and the gas escapes through the water in large
bubbles, passing thence through a glass pipe inclined at an angle at the top of the lead pipe
into the air. When sufficient gas has escaped to reduce the pressure to the working limit the
pipe is automatically sealed.

All rubber junctions are covered with calico, and painted, and where practicable secured
with copper wire.

The main advantages of this process are its quick turnaround time, size of the charge that
can be from 20 kg to as large as you like. The rotating lances are made from temperature
resisting ceramics for long life and evenly introduce chlorine to the melt. The use of modern

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induction furnaces keeps the consumption low using far less kilowatts then coil type
furnaces for the same size of melted product.

In this process the gold produced is 99.95 Fine that is good enough for most commercial
purposes. Most of the metals remaining in the gold are mostly silver and copper that if
desired can be removed using the Wohlwill Process producing gold bullion that is 99.999
Fine.

Passing the Gas Through the Molten Metal

The guard with the clay liner is placed in the furnace, and 2 or 3 ounces of fused borax added.
It is heated until dull red. The ingots are then added, the weight of these being about 700 oz.
Fuel is added, and the dampers opened. As soon as the gold is melted, the lid is put on and
the pipe stem, carefully annealed and heated to bright redness, is pushed to the bottom of
the pot, chlorine at the same time being gently turned on to avoid the plugging of the tube
through the gold solidifying in it.

The supply of chlorine is adjusted so as to avoid projection of globules. This can be told by
feeling the pulsations of the rubber—when the gold contains much silver or base metals the
absorption of the chlorine takes place rapidly but quietly, very little motion of the molten
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metal being apparent, but near the end of the operation the gas must be admitted in a fine
stream only. The chlorine is not dried before it passes into the gold, but the small amount of
water vapor present does not affect the operation. It was formerly the practice to dry the gas
with strong sulphuric acid, but this has been abandoned as unnecessary.

The order in which the metals chloridise has never been determined. Iron appears to come
off separately, and is attacked at the commencement, while silver and copper remain and
come off practically together.

When the bullion contains much base metal the consumption of chlorine is greater, and the
time occupied longer, but not in proportion to the amount contained, since a more rapid
stream of chlorine can be safely admitted than when the base metals and silver are nearly all
removed.

The usual time allowed is four hours for a pot containing about 700oz. of bullion. If the
bullion is nearly fine a much shorter time would suffice; for instance, 2 per cent, of silver and
0.5 per cent, of base would take about 1½ hours; 3.5 of silver and 1.5 of base, two hours.

Owing to the presence of air at first in the chlorine mains the stream admitted is slow at first,
otherwise there is danger of spitting.

When the operation is nearing completion, the flame issuing from the holes or slit in the lid
becomes small, and alters in appearance; it becomes very luminous, has a brown edge, and
if a white, rough, cold surface is plunged into it will become coated with a yellowish-brown
tinge. It consists mainly of ferric, chloride, with traces of silver chloride and gold. As soon as
this stain appears the current of gas is reduced, and allowed to pass in for another 15
minutes, when the clay pipe is withdrawn, and the clay pot lifted out of the guard pot. The
pot is allowed to stand under a hood to carry off the fumes until the gold has solidified. The
liquid chloride and fluxes are then poured into a Mould provided with a hood. The pot is then
broken, and the cone of gold dropped into the guard pot, and cast into two flat ingots, 12 by
4 by 1½ inches. These bars, while still hot, are dropped in dilute sulphuric acid, and then
water, and are still hot enough to become dry.

A modification of the process has been introduced. After the chlorine has been passed into
the bullion for some time the chloride of silver which forms occupies twice the space that the
silver did, and rises in the pot. When much silver was present the chloride was ladled out
from time to time, to prevent it overflowing, and poured into a Mould on top of the furnace.
This practice has now been adopted for all the bullion. The chloride is bailed out in such a
way that any drip falls back again into the crucible. When the chloride film becomes thin
some gold is also picked up—the last pouring's are, therefore, put into a separate Mould,
when the gold present solidifies, the chloride is poured off, and the gold returned to the
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crucible. The last portion of silver remains on top of the gold, bone ash is added to thicken it,
after which the refined gold is stirred and poured, the pot being returned at once to the
furnace to be used for a fresh lot of bullion.

The chlorides contain 5 to 10 per cent, of gold in feathery particles. Generally speaking, the
gold is not present as chloride when the chlorine is passing, but chloride of gold has been
found in the silver chloride when the process has been experimentally carried too far. The
chlorides are supersaturated with chlorine and this is copiously evolved on cooling. To
recover this gold 7 per cent, of their weight of bicarbonate of soda is added cautiously and
without stirring, which produces a shower of globules of reduced silver, and these, falling
through the chlorides, carry down nearly all the gold; another lot is needed to carry the
balance down. The pot is lifted out, the button allowed to settle and solidify, when the
chlorides are poured into a Mould 12 by 10 by 2 inches. The silvery button obtained contains
from 40 to 60 per cent, of gold. The gold in bars and in the buttons contain 99.85 per cent, of
the gold issued for refining, the balance being practically in the pot. The maximum quantity
left in the silver is 1 part in 10,000, but it is usually from half to one-third of this quantity.

Wohlwill process:

Hans Emil Wohlwill, a German engineer, invented the Wohlwill Process in 1874. Unlike the
Miller Process, which is known among refineries as a relatively cheap and easy way to
produce high-purity gold (in the 99.95% purity range), the Wohlwill Process is complex and
expensive. But when done correctly, it can produce gold samples of 99.999% purity.

The Wohlwill Process has three main components:

• The anode – an electrode through which electric current flows into a polarized
electrical device
• The cathode – an electrode through which electric current flows out of a polarized
electrical device
• The electrolyte – an electrically conductive substance (standing in for a polarized
electrical device)

Each of these components contains gold. The anode is made of somewhat impure gold –
about 95% purity or higher (lower purity will reduce the efficiency of the procedure). The
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cathode is made of pressed 24k gold sheets. The electrolyte is pure chloroauric acid, made
by dissolving gold in a powerful acid called aqua regia.

With these components properly set up, an electric current is applied. Electricity travels
from the anode, through the conductive electrolyte, and into the cathode. When this occurs,
the gold in the impure anode dissolves and its ions travel though the chloroauric acid, then
electroplate or “stick” to the 24k gold cathode. This continues until the anode completely
dissolves. The ultra-pure gold that collected on the cathode is melted down to whatever
specification the application demands.

The Wohlwill process is an industrial-scale chemical procedure used to refine gold to the
highest degree of purity (99.999%). The process was invented in 1874 by Emil Wohlwill.
This electrochemical process involves using a cast gold ingot, often called a Doré bar, of
95%+ gold to serve as an anode. Lower percentages of gold in the anode will interfere with
the reaction, especially when the contaminating metal is silver or one of the platinum group
elements.

The cathode(s) for this reaction are small sheets of pure (24k) gold sheeting or stainless
steel. Current is applied to the system, and electricity travels through the electrolyte of
chloroauric acid. Gold and other metals are dissolved at the anode, and pure gold (coming
through the chloroauric acid by ion transfer) is plated onto the gold cathode. When the anode
is dissolved, the cathode is removed and melted or otherwise processed in the manner
required for sale or use. The resulting gold is 99.999% pure, and of higher purity than gold
produced by the other common refining method, the Miller process, which produces gold of
99.95% purity.

For industrial gold production the Wohlwill process is necessary for highest purity gold
applications. When lower purity gold refines often utilize the Miller process due to its
relative ease, quicker turnaround times, and because it does not require a large inventory of
gold, in the form of chloroauric acid, on site at all times.

The process was first invented by Emil Wohlwill in 1874 in Hamburg and has been known
as one of the most popular procedures for gold purity ever. The process sees impure gold
cast into anodes of 100 ounces. These anodes are usually suspended in porcelain cells awhile
this is happening cathodes are thin strips of pure gold. Using an electrolyte solution, an
electric current us passed through the anode to the cathode, which results in the anodes
being slowly dissolved and the gold that is within in anodes gets deposited onto the cathodes.

Any other metals such as silver will precipitate to the bottom of the cells leaving the cathode
pure gold. The process usually takes around two days and is still not complete at this point.
Now that the gold has all been transferred to the cathodes, they will still have to be removed,
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melted and eventually cast into gold bards. This initial procedure allows for purity of up to
99.95 % purity. However further processes that are usually part of the overall Wohlwill
process that will allow you to reach 999.9% purity. The fact that this process was so effective
at removing and impurities from the gold is the reason that was able to be so successful.

An old and well-established process, the Wohlwill method is widely used in major gold
refineries, often in conjunction with the Miller process. (For typical jewelers scraps and
wastes, a preliminary refining step, such as the Miller or inquartation process, is required.)
An electrolytic refining technique, it entails the electrolytic dissolution of an impure gold
anode in a hydrochloric acid-based electrolyte. The process results in a deposition of 99.99
percent pure gold at the cathode.

The silver and insoluble PGMs (along with a little gold) fall out as anode slimes, with the
silver precipitated out as silver chloride, and all are recovered later. Any base metals,
platinum, and palladium remain in solution, and can be treated later to recover the PGM.
Gold of a purity of at least 98.5 percent is normally required for the anode, as too much silver
will result in silver chloride building up on the anode surface and preventing dissolution of
the gold. Typically, the input material for the anode is the gold from the Miller process,
described previously. The main reason is time consuming-typically 24 hours or more-and
suffers from the lock-up of gold inventory in the electrodes and electrolyte, the Wohlwill
process is not suitable for small-scale refining.

With these components properly set up, an electric current is applied. Electricity travels from
the anode, through the conductive electrolyte, and into the cathode. When this occurs, the
gold in the impure anode dissolves and its ions travel though the chloroauric acid, then
electroplate or “stick” to the 24k gold cathode. This continues until the anode completely
dissolves. The ultra-pure gold that collected on the cathode is melted down to whatever
specification the application demands.

This is a very expensive procedure – especially because it takes gold to make gold. To
perform the Wohlwill Process, a refiner must have enough gold for anodes and cathodes.
They also must have large amounts of gold on hand to convert to chloroauric acid
(fortunately, this process is reversible). Because of the complexity and cost of the Wohlwill
Process, it’s used only for specific applications. Instead, most refiners prefer to use the Miller
Process to create high-purity gold.

A variant of the Wohlwill process is the fizzer cell. In a fizzer cell, the decaying anode is
surrounded by a ceramic cell through which Electric current can pass, but dissolved ions
cannot. To recover gold from a fizzer cell, one removes the gold chloride-laden solution and
selectively precipitates the gold using a selective reducing agent such as ferrous sulphate,
hydrazine which is highly dangerous and explosive, or other lixiviants.
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A fizzer cell which utilizes a carbon rod instantly introduces contaminants into the solution.
Carbon rods through which electrical current passes, begin to break down immediately upon
application of current. This perceptibly worsens contamination of cell over time.

This is a very expensive procedure – especially because it takes gold to make gold. To
perform the Wohlwill Process, a refiner must have enough gold for anodes and cathodes.
They also must have large amounts of gold on hand to convert to chloroauric acid
(fortunately, this process is reversible). Because of the complexity and cost of the Wohlwill
Process, it’s used only for specific applications. Instead, most refiners prefer to use the Miller
Process to create high-purity gold.

The major established technology for the production of high purity gold is the Wohlwill
electrorefining process8,9. In a typical operation, the impure gold is cast into anodes and
electro-refined in an HCl/HAuCl4 electrolyte. The average lifetime of an anode is 22 h, after
which time the remaining anode material is recycled. A gold purity of 99.99% is typically
achieved.

The lock-up of gold in the Wohlwill process is substantial because of the necessity to cast
anodes, the high concentration of gold in the electrolyte (approximately 100 g/l), and the
significant recycling of gold in the circuit, both through spent anodes (~25%) and as losses
to the anode slimes (up to 30%). The Minataur Process has a significant advantage in
reducing both the residence time of the gold in the circuit and the amount of gold recycled.
Purities higher than 99.99% can be produced if required.

The present cost to Harmony Gold Mine of refining gold, including smelting to produce Doré
bullion, is R267/kg. It has been estimated that the implementation of the Minataur™ Process
will contribute to an annual saving of R3.6 million in operating costs for the mine.

The Wohlwill process can create 99.95% pure gold, while the Miller process can create
99.5% gold purity. The Wohlwill process is an electrolytic process wherein essentially pure
gold coats a cathode, and wherein impurities such as silver form chlorides and remain near
the anode. Typically, Pt and Pd also dissolve in the electrolyte. In the Miller process, silver
and other metals are converted to chlorides by passing chlorine though molten dore, and
then are poured off or volatized. The Miller process creates a purity of only about 99.5%,
since it is stopped before the gold converts into a chloride.

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
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migrates under the influence of the electric field to 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.

Extraction of Gold from Electronic waste

The amount of gold recovered from one ton of e-waste consisting of personal computers only
is very much large. It is estimated that this amount is greater than that recovered from 17
ton of gold ore. Literally, e-waste is a rich source of precious metals (PMs) compared to their
primary ores. The dumping of e-waste has multiple disadvantages including the pollution of
underground water and soil, and wasting a big source of valuable metals. In order to meet
the environmental norms for hazardous waste disposal and conservation of natural
resources globally, there is a rising anxiety for the safe recycling of e-waste with greater
usage of electronic and electrical gadgets and devices. The dumping of e-waste has multiple
disadvantages including the pollution of underground water and soil, and wasting a big
source of valuable metals. In order to meet the environmental norms for hazardous waste
disposal and conservation of natural resources globally, there is a rising anxiety for the safe
recycling of e-waste with greater usage of electronic and electrical gadgets and devices. Now
a days, the different techniques that can be adopted for extraction of precious metals are
mechanical processing, pyro-metallurgy, hydro-metallurgy, bio-leaching or a combination of
these techniques, with main focus on extraction of gold, chemical and hydro-metallurgical
processes must be adopted.

In hydro-metallurgical process the below given process may involve in the extraction of gold.

Cyanide Leaching m
In cyanide leaching, the following reactions may involve:
• 4Au + 8CN → 4 Au (CN) 2- +4e
• O2 + 2H2O + 4e- → 4OH−

The cyanide solution percolate to the ore which contained in columns or heaps. Gold is
dissolved by the cyanide and then removed from the heap or columns. This is then extracted
from the leach solution by adsorption of carbon. This cost-effective, proven method of ore
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extraction provides maximum recovery for many gold ores, including low grade and some
refractory ores. Heap leaching facilitates the profitable extraction of gold from very low-
grade ore.
Prior to heap leaching, crushed ore is heaped into structures 10 to 20m. A dilute cyanide
solution is sprayed on the heap, percolates through the pile and dissolves the available gold.
The solution is then directed into a pond. The cyanide solution, which is said to be “pregnant”
with gold, is then pumped through columns where the gold is recovered. Activated carbon
effectively removes the gold from the cyanide.

Halide Leaching
In halide leaching Gold makes both Au (I) and Au (III) complexes with chloride, bromide and
iodide depending on the solution chemistry conditions.
• 2HNO3 + 6HCl → 2NO + 4H2O + 3Cl2
• 2Au + 11HCl + 3HNO3 → 2HAuCl4 + 3NOCl + 6H2O

Thiourea Leaching
The thiourea ((NH2)2CS) leaching is considerable for the extraction of gold. In acidic
conditions, thiourea dissolves gold, forming a cationic complex; the reaction is rapid and gold
extractions of up to 99% can be achieved.

Au + 2CS (NH2)2 → Au (CS (NH2)2) 2+ + e - rec

Thiosulphate Leaching
Thiosulfate is used widely in photography and in the pharmaceutical industries. This is the
substitute for the cyanide. The Gold is dissolved in the ammoniacal thiosulfate solution with
the presence of cupric ions. This mechanism of gold leaching was determined by the
Aylomore and Nir. It is also known as the electrochemical-catalytic mechanism. It was
proposed that Cu (NH3)4 2+ species present in solution acquires electrons on the cathodic
portion of the gold surface and is directly reduced to Cu (NH3)2+. At the same time, either
ammonia or thiosulfate ions react with Au+ ions on the anodic surface of gold then they enter
the solution to form either Au (NH3)2+ or Au (S2O3)23- .

Au + 5S2O3 2- + Cu (NH3)4 2+ → Au (S2O3) 3- 2 + 4NH3 + Cu (S2O3) 5- 3

2Cu (S2O3) 5- 3 + 8NH3 + ½ O2 + H2O → 2Cu (NH3) 2+ 4 + 2OH- + 6S2O3 2-

Aqua Regia
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Aqua regia leaching was selected by Sheng and Etsell for recovery of gold from computer
chips due to its flexibility, ease and low capital requirement. Gold leaching involved three
stages. During stage I, computer chips were separated from the printed circuit boards by
leaching. Stage-I leaching was conducted in nitric acid systems, in which the effects of acid
concentration, temperature, pulp density and retention time were investigated. After stage-
I leaching, the computer chips and coagulated epoxy resin were mechanically crushed. Stage
II leaching used the optimized parameters from stage-I. The third stage leach dissolved
metallic gold with aqua regia from the second stage leach computer chip residue. The
parameters, such as temperature, pulp density, and retention time, were studied. It was
concluded that higher temperatures tend to give faster leaching rates of gold. The amount of
aqua regia required for complete immersion of the computer chips was approximately 2ml
per gram of computer chips. Increasing aqua regia beyond this ratio did not increase the
leaching rate of gold. Agitation was unnecessary for gold leaching in the aqua regia solution.
The self-induced agitation brought about by the release of nitrous oxide and chlorine vapors
caused bubbling and frothing of the aqua regia solution.

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 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 catalysts employed in the production of nitric acid.

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How much gold is left?

Experts have estimated that we have less than 55,000 tons of gold left to discover. Even so,
we cannot be sure how much of this amount is extractable. We know that the earth’s crust is
gold in a proportion of about four parts per billion. We also know that gold can be found and
extracted from the ocean, which is believed to contain about 10,000 tons of gold. Even the
continent of Antarctica is known to have large deposits of gold buried deep within the ice.

It is technically possible to extract gold from other elements. As such options become more
technologically refined, we may never truly run out of gold. As things currently stand, we
know that not all of the gold that exists in the Earth’s crust is in large enough portions to be
found and mined. Extracting gold from the ocean, for instance, is not cost-effective, and the
deposits we know of in Antarctica are trapped by ice and guarded by extreme weather
conditions, making them dangerous and expensive to reach. Extracting gold from other
elements is also incredibly expensive, but more than that, the process results in gold that is
too radioactive for safe use by humans. With these options ruled out, our only hope is to find
new underground reserves of gold.

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