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Developments in Gold Leaching: A Literature Survey


a a b
A. R. UDUPA , S. K. KAWATRA & M. S. PRASAD
a
Department of Metallurgical and Materials Engineering , Michigan Technological University ,
Houghton, Ml, 49931
b
Mineral Resources Research Center , University of Minnesota , Minneapolis, MN, 55455
Published online: 27 Apr 2007.

To cite this article: A. R. UDUPA , S. K. KAWATRA & M. S. PRASAD (1990) Developments in Gold Leaching: A
Literature Survey, Mineral Processing and Extractive Metallurgy Review: An International Journal, 7:2, 115-135, DOI:
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Developments in Gold Leaching:


A Literature Survey
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A. R. UDUPA*, S. K. KAWATRA* AND M. S. PRASAD**


• Department of Metallurgical and Materials Engineering, Michigan Technological University,
Houghton, Mf 49931
•• Mineral Resources Research Center, University of Minnesota, Minneapolis. MN 55455

Received April 5. 1990; in final form July 12. 1990

The gold industry has seen intense activity in the areas of exploration and metallurgy in recent years.
Many developments have taken place through which ore bodies that were once considered uneconomical
to exploit are becoming economical grade. Even the traditional cyanidation process has been modified
during the course of time to make it more economical and efficient. Developments such as heap leaching,
in-situ leaching, carbon-in-pulp (CIP). carbon-in-leach (Cll.), resin-in-pulp (RIP), and pretreatment of
refractory ores have already made an impact on gold industries. Research and development work is
also being carried out on less toxic. more efficient lixiviants which may eventually replace the toxic
cyanide. solving the disposal problem currently facing the industry. This paper aims at summarizing
the developments in the extraction of gold using conventional. as well as unconventional. lixiviants.
Some developments in the area of gold recovery from pregnant solutions have also been brieflydiscussed.

KEY WORDS: Gold leaching. developments; Refractory ores; Oxidation; Heap leaching; Thiourea;
Cyanidation; Chlorination; Carbon-in-pulp.

INTRODUCTION

Gold. a high value element widely distributed in a number of geological environ-


ments in recoverable amounts. has been known to mankind for millennia. Due to
continued buoyant demand and a relatively high. stable price. gold has been the
focus of intense activity in the areas of exploration and metallurgy in recent years.
The total worldwide output of gold in 1988 increased to 59.5 million ounces, an
increase of about 10% over the previous year (Table I). During the same period,
the United States has witnessed an increased output of over 32% and stands as
the third largest producer in the world.
Processes for the extraction of gold have improved dramatically over the years.
The latest developments in extraction technology have not only reflected the ec-
onomic aspects in terms of increased efficiency and reduced costs but also the
environmental aspects, particularly with regard to ·gaseous emissions and liquid
effluents discharged from gold plants. Ore bodies that were at one time considered

115
116 A. R. UDUPA. S. K. KAWATRA AND M. S. PRASAD

TABLE I
World gold output

Million oz.

Country 1987 1988


South Africa 19.2 19.9
Soviet Union 8.9 9.0
United States 4.9 6.5
Australia 3.5 4.9
Canada 3.7 4.1
Brazil 2.7 3.2
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China 2.3 2.5


Papua New Guinea 1.1 1.2
PhilIipines 1.0 1.1
Poland 1.1 1.0
Other 5.7 6.1
TOTAL 54.1 59.5

Source: Ref. 133

uneconomic to mine and mill are becoming economic grade due to new and ad-
vanced extraction techniques. Figure l' summarizes various treatment options avail-
able for the extraction of gold'. Of these, cyanidation still remains the most common
method of extraction of gold from free-milling types of ore. However, most of the
gold extracted now is from refractory ores, and direct cyanidation cannot efficiently
recover gold from such ores. Thus the problem of winning precious metals from
troublesome ores is attracting all aspects of applied mineral research and devel-
opment. Furthermore, there is a general interest in replacing cyanide by lixiviants
which are nontoxic and environmentally safe. Recently numerous review papers
describing the history of gold metallurgy", the processing of refractory gold ores1.3.4·s,
and the dissolution chemistry of gold and silver in different lixiviants" have been
published.
The aim of this paper is to attempt complete disclosure of the state-of-the an in
the extraction of gold, and to review conventional cyanidation of both free milling
and refractory ores, as well as gold extraction using unconventional lixiviants.

TREATMENT OF FREE MILLING ORES


Gravity methods such as jigs, tables, moving belt separators, etc., are used to
recover relatively coarse gold from placer deposits which do not readily respond
to flotation or cyanidation. This technique is also used for non-placer deposits to
assist flotation and cyanidation. Flotation has been found to be quite effective for
free gold and silver found in some ores and tailings. These concentrates are sent
to smelters for further processing using cyanidation after regrinding and roasting,
if necessary,
Conventional Cyanidation
More than 87% of the gold extracted in the United States in 1988employed classical,
direct cyanidation 7 . This process, ideal for free milling. nonrefractory ores. is shown
DEVELOPMENTS IN GOLD LEACHING: A LITERATU~E SURVEY 117

Gold ore
..--_1__...,
I i
Free milling ore
cony. leaching Refractory
ore

I I
Pretreatments and Direct Au
Au leaching leaching
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I
I I
Non.conv. I
Carbon-in-leach Alkaline
IIxlvants cyanldatlon
(CIU (e.g. thiourea, under 02
malonon Itrltel pressure

Roasting Blo-oxidatlon Chemical'


oxlctatlon

I
Oxidative AlkJline Adld
acid leaching pressure pressure
leaching leaching
FIGURE 1 Different treatment methods for extraction of gold I.

in Fig. 2. Ore is first ground by conventional multistage crushing and ball milling,
or by semi-autogenous grinding (SAG), then is leached in agitated or Pachuca-
type tanks, using lime, dilute cyanide solution and oxygen. The leached pulp then
undergoes counter-current-decantation (CCD) or filtration, using drums or belts.
The precious metal values are finally precipitated from the pregnant leach liquor
using zinc dust (the Merrill-Crewe process); or are electodeposited on a steel wool
cathode. The overall chemical reactions are:

Leaching: 4Au + 8NaCN + 0, + 2H,O = 4NaAu(CN), + 4NaOH


Merrill-Crewe 2NaAu(CN), + Zn = Na,Zn(CN). + 2Au
precipitation:
40H- = 0, + 2H,O + 4e-
Electrodeposition { 2e- + 2Au(CN), = 2Au + 4CN-

Direct alkaline cyanidation is applicable only to free milling ores. If the ore is
refractory, a pretreatment step is necessary to make it amenable to cyanide leaching.
Developments in the treatment of refractory ores are discussed below.
118 A. R. UDUPA. S. K. KAWATRA AND M. S. PRASAD

GOLD/SIl..VER ORE OR CALCINE

J
CYANIDE LEACHING

.- SOUD/UOUID
SEPARATION
PULP
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TAIL INGS
TOWASTE

ACTIVATED ION EXCHANGE


CARBON RESIN
CIRCUIT CIRCUIT

CLEAR CONCENTRATED SOLUTION I TAJUNGS


+ TOW ASTE

+
ZINC DUST
I
CEMENTATION
I ELECTROWINNING

+ GOLD/SILVER SPONGE ~

DORE BULLION

FIGURE 2 General flowsheet for the extraction of gold through cyanidation 3.

TREATMENT OF REFRACTORY GOLD ORES

Gold ores which are not amenable to standard cyanidation even after fine grinding
are termed refractory ores. A detailed analysis of various causes of refractoriness
is reported by Jha", Gold is extracted from such ores by pretreating or by employing
modified cyanidation processes. If the refractoriness is due to the' presence of
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 119

sulfides, an oxidation pretreatment is given to make the ore amenable to cyan i-


dation. The method of oxidation may be simple roasting, chemical oxidation,
oxidation under pressure in an autoclave, or bacterial oxidation. If performed under
regulated conditions, oxidation treatment can also oxidize organic matter, arsenic
and tellurium. '

Simple Roasting
Roasting is generally carried out in a fluidized bed roaster, at a temperature between
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450·C and 750·C with an ample supply of oxygen. Close temperature control is
essential for ores containing both sulfides and carbonaceous materials in order to
avoid the loss of gold either from preg-robbing' or from ferrites formed from any
copper, nickel, lead, and antimony present in the ore. Because of economics, it is
imperative that the roasting be autogenous. In order to achieve this, the ore should
be reasonably high in sulfur and carbon content or it should be amenable to
concentration. In practice, because of the fine dissemination of the gold, concen-
tration may not always be feasible, as in the case of Mercur', Carlin", Jerritt
Canyon!", or McLaughlin I I ores. Roasting also produces gases containing sulfur,
antimony, arsenic and mercury which must be controlled at environmentally ac-
ceptable levels using devices such as electrostatic dust precipitators, bag houses,
or high efficiency scrubbers, which are expensive. Alternative commercially viable
methods of oxidation have now been developed which eliminate the problems
associated with oxidative roasting. These include chemical oxidation, pressure ox-
idation, bio-oxidation and, more specifically for,antimonial products, high pressure I
low alkalinity cyanidation.

Chemical Oxidation
Chemical oxidation is carried out either at ambient pressure or under pressure.
Commercial application of chemical oxidation was first applied at the Carlin Mines
to treat carbonaceous ores", The flowsheet included a double oxidation method:
first, aeration in the presence of sodium carbonate and, second, by chlorination.
The amount of chlorine consumed was about 36 kilograms per ton of ore". Pre-
leaching the gold ore with sulfuric acid or ammonium hydroxide to remove copper
or antimony before cyanidation in the presence of air or oxygen at ambient pressure
was reported by Nagy et aPJ. Lakshmanan and Childs applied Caro's acid (HlSO S)
for the oxidation of gold-bearing arsenopyrite ores, tailings and concentrates to
obtain improved extraction of gold", The recently developed NITROX process,
which treats the ore for 1 to 2 hours in nitric acid in the presence of air at atmospheric
pressure to oxidize pyrites and arsenopyrites prior to cyanidation, claims to increase
the gold recoveries from 30% to over 90%15, ,
Aqueous chlorine or hypochlorite oxidation has been demonstrated to be an
effective pretreatment process for the carbonaceous type of refractory gold
ores ll,IJ,I6-11. Scheiner et aP7. have demonstrated from bench-scale and pilot-scale
experiments that a sodium hypochlorite pre-leach of Carlin-type carbonaceous
refractory gold ores followed by cyanidation improved the gold extraction to >90%,
120 A. R. UDUPA, S. K. KAWATRA AND M. S. PRASAD

compared to 6-32% extraction by cyanidation of the ore alone. G uay12,22 obtained


>85% extraction of gold from Carlin-type carbonaceous pyritic gold ores through
double oxidation consisting of initial air oxidation at 80-86°C followed by chlorin-
ation of the aqueous slurry.

Chlorination
Newmont Mining Corporation and the U.S. Bureau of Mines have developed the
chlorination process to oxidize ·the carbonaceous content of the gold ore prior to
cyanidation, and the process has been successfully employed at Carlin Mines since
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the early. 1970's. In a recent study, Newmont Mining Corporation reported a flash
chlorination technique where the chlorination chemistry is optimized to achieve an
average 6% increase in gold extraction with 25% per ounce reduction in chlorine
consumption at a lower operating cost", Recent pilot plant tests have shown that'
both sodium hypochlorite and chlorine oxidize carbonaceous ore, yielding a gold
extraction of >90% when cyanided, compared to only 6-32% recovery obtained
by direct cyanidation". Barr and coworkers" have reported substantial increases
in the recovery of gold from refractory ores from Nevada after chlorination oxi-
dation (Table II). Freeport McMoran Gold Co. at its Jerritt Canyon project area
in Nevada has employed chlorination to treat 4000 t/day of carbonaceous ores
prior to gold extraction via the carbon-in-leach process. The chlorination step
improved the overall gold dissolution to 90-92% with final recoveries of 89-90%20.
Recent pilot plant tests have shown that slow addition of chlorine and the addition
of sodium hydroxide or lime increased the extraction of gold on cyanidation, while
minimizing the emission of chlorine".
Another development is the generation of in situ hypochlorite ion in the ore
pulp by electrooxidation. The technique consists of adding NaCI to the pulp and
passing electric current through electrodes placed in the pulp!'. If the ore is re-

TABLE II
Effect of chlorination oxidation on selected ores

Chlorination

Sulfide Organic Oxidized


Ore Gold Sulfur Carbon Soda Ash Ore Gold
Classifi- Recovery Destruction Destruction Consumption Recovery
Ore cation (%)' (%) (%) (kg/t) (%)
Hanson Creek Oxide 90.0 95.5 56.0 0.0 85.0
Limes/one
Hanson Creek Refractory 47.0 50.0 53.0 0.0 90.0
Limestone
Roberts Mts. Refractory 13.0 42.0 57.0 98.0 88.0
Siltstone
Hanson Creek Oxide 81.0 95.0 41.0 13.0 85.0
Jasperoid
Permian >100.0 81.0
Refractory 13.0 82.0 35.0
Overlap

• Recovery from carbon-in-leach process without chlorine pretreatment.


Source: Ref. 23
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 121

fractory due to carbonaceous material alone, blanking agents such as paraffin oil,
aerosol OT, phenol iodine, or RV-2 (p-N02-benzoazo-salicyc!ic acid) would be
effective to suppress its preg-robbing propertyt-". Royston et al. 25 reported im-
proved extraction of gold (60-70% against 25-30% obtained during conventional
cyanidation) from Porgera pyrite concentrates using air as an oxidizing agent in
the presence of sodium hydroxide, sodium carbonate, or calcium hydroxide. Corn-
well and Hisshiou" reported significant improvement in gold recovery at Emperor
Mine in Fiji after using sodium hydroxide or sodium carbonate with Ca(OCl)2 to
treat telluride concentrate.
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Pressure Oxidation
Aqueous pressure oxidation of refractory gold-bearing sulfides has been investi-
gated for the last 30 years. Sulfides are normally oxidized in either alkaline or
acidic media in the presence of oxygen at a temperature in the range of 170-190·C,
pressure 1500-2000 kPa, 2 hour retention time, and 40-50% solids in the pulp".
Aqueous pressure oxidation carried out on several sulfide ores and concentrates
by Sheritt Gordon resulted in gold extraction ranging from 87-98.5% for ores and
92.4-99.4% for concentrates". Similar results were also obtained by investigations
carried out at AMAX laboratories on Porgera" and Mcl.aughlin" ores. Autoclave
oxidation was first included in commercial circuits by Homestake for its Mcl.auglin
project". The oxidation at McLaughlin is carried out at a pH of 1.8 to 1.9 (acidified
by the addition of sulfuric acid) in an autoclave in the presence of oxygen (35-45
kg/t of slurry) under a pressure of 2200 kPa. The pH of the slurry coming out of
autoclave was raised to 10.8 prior to cyanidation. The recovery of gold was reported
to be 92-93%, which is much higher than 5-80% recovery obtained by direct
cyanidation". Pressure oxidation has been used in the ~ow sheet of Porgera Gold
project, PGNJ2, and is also used at the Sao Bento gold project in Brazil". The
ARSENO process of Bacon, Donaldson and Associates Ltd., which consists of
leaching the concentrate under 1380 kPa oxygen pressure at 60-120·C for 15 min-
utes, claims to recover 98% or better from sulfide concentrates after cyanidation'"?'.
Dry and Coetzee" reported a process to recover gold from pyrite-arsenopyrite
concentrates. The process involves heating the pyrite and arsenopyrite in the ab-
sence of oxygen at 6OO·C, which results in their thermal decomposition to gaseous
elemental sulfur, arsenic and arsenic sulfides. with a solid residue of pyrrhotite.
Oxidative leaching of the pyrrhotite to elemental sulfur is undertaken at a tem-
perature of 1OO·C and a pressure of 500 kPa for 5 hours followed by sulfur removal
and conventional cyanidation.
Pressure oxidation of gold from ores or concentrates under alkaline conditions
has also been investigated by many workersJ9-42. High pressure low alkalinity cyan-
idation has been found commercially applicable in treating highly refractory an-
timonial products especially stibnite concentrates. The process involves the batch
cyanide leaching of 20-22 tons of concentrate at a pressure of 8.8 MPa and pH of
7 in a pipe reactor. Oxygen is injected into the reactor at a pressure of 12.0 MPa.
The total treatment time per batch is approximately 135 minutes. Gold extraction
of 82-87% has been achieved, as compared to lower levels of extraction using
conventional cyanidation.
122 A. R. UDUPA. S. K. KAWATRA AND M. S. PRASAD

The autoclave oxidation of high sulfur or high carbon gold-bearing sulfide ores
poses some problems. High sulfuric acid production during autoclave oxidation of
high sulfur ore not only requires a bigger autoclave but also increases the cost of
neutralization. Gold ore containing high organic content when oxidized in an au-
toclave below 20DoC results in preg-robbing as experienced at Mercur". However,
if the temperature is between 200-250°C, the cost of autoclaving and the cost
associated with bleeding of gases are excessive.

Bio-Oxidation
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The ability of certain bacteria (e.g., Thiobacillus ferrooxidans and Tithiooxidansi


to oxidize gold-bearing sulfide minerals such as pyrite, arsenopyrite, and base metal
sulfides is vigorously pursued by various organizations throughout the world. In
the case of pyrite, the following equations describe the typical reactions that occur
in a bacterially catalyzed oxidation system:
2FeS, + 70, + 2H,0 = 2FeSO, + 2H,SO,
4FeSO, + 0, + 2H,SO, = 2Fe,(SO,), + 2H,0
FeS, + Fe,(SO,), = 3FeSO, + 2S"
2S0 + 2H,0 + 30, = 2H,SO,
Fe,(SO,), + 6H,0 = 2Fe(OH), + 3H,SO,
The application of bacteria for the oxidation of pyrite and arsenopyrite concen-
trates from the Porgera and Cenola mines has been demonstrated by Lawrence
and Bruynesteyn of B.C. Research":", who reported that an extraction as high as
94% for gold and 99% for silver could be obtained from pyrite concentrates,
whereas conventional cyariidation had recovered only 60-78% gold and 80-86%
silver. Hutchins et al", obtained 83-93% gold recovery after a pretreatment with
the facultative thermophile S161 from carbonaceous ores yielding 10-15% gold
recovery by direct cyanidation. Fridman and Savarr" reported successful application
of bacteria for treating arsenopyrite concentrates. Bacterial leaching did not oxidize
the organic matter, and therefore a resin-in-leach cyanidation was used. Generally,
bio-oxidation pretreatment of refractory ores was carried out in dumps or heaps.
However Davy McKee reported to have developed a leaching process using an
agitated tank and claimed to have obtained an average of 90% gold recovery in
less than 72 hours at ambient temperature and pressurev-".
Marchant'" summarized Austin Gold Venture's bio-leaching tests, which included
a suggested flowsheet for 18 tpd and 36 tpd bio-leaching installations at the existing
gold mill, and reported >90% extraction by CIL cyanidation. Gilbert et al. ,51 while
comparing the technical performance and economics (capital.cost, revenue, op-
erating cost, etc.) of bacterial pre-oxidation and a classical roasting approach for
treating a specific auriferous pyrite concentrate, concluded that the rate of return
will increase to 10% in 10 years for bio-oxidation compared to only 2.6% for
conventional roasting. It has been reported that two small-scale (10-15 t/day)
commercial bio-leaching plants are operating in South Africa" and one plant (5 tl
day) in Zimbabwe". With the introduction of the bio-oxidation circuit in South
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 123

Africa, gold recovery has been increased from 35% (direct cyanidation) to above
95%52.

HEAP LEACHING

Heap leaching has been employed for gold ores since the late 1960's and is gaining
increased interest throughout the world especially for exploiting low-grade ores,
mine waste materials, or deposits too small to justify the construction of a con-
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ventional milling and recovery facility. Although the conventional processing plants
still produce more gold, heap leaching accounts for the majority of operations in
the western U.S. 54 • Heaps of five thousand to two million tons grading as low as
0.79 glt have been successfully leached for gold".
In spite of its applicability to low-grade ores, heap leaching suffers from draw-
backs such as long leaching time, low permeability due to the presence of clayey
or mixture of coarse and fine particles, and, in some cases, seasonal operation due
to cold climate. The problem of long leaching time and low permeability is ad-
dressed, to some extent, by agglomeration of the ore prior to heap leaching, as
practiced in Kernco's McLean Mine near Tonopah, Nevada". To avoid the loss of
percolation by the compaction of the top surface caused by conventional radial
stackers, specialized stackers or conveyor transport and conveyor stackers have
been used. The conveyor system is currently being used at the Florida Canyon
Nevada mine of Pegasus Gold Corporation",
When the temperature falls below lOoC in countries with a cold climate, the
solubility of gold in cyanide solution decreases sharply making heap leaching dif-
ficult to operate. The main development to extend the leaching season, therefore,
involves heating the leach solution prior to adding it to the heap. Heating of leach
solution is being practiced at the Smokey Valley Mining Company gold operation
in Nevada", where barren solution from the carbon adsorption circuit is heated
from 4°C to 15°C via an oil-fired heat exchanger before being returned to the leach
pads. However, a submerged heating system tested at the Alligator Ridge gold
plant in Nevada did not prove to be cost effective and was discontinued.
In order to avoid oxygen depletion, and hence improve gold dissolution kinetics
at the core of the heap, Worstell 58 proposed injection of oxygen. Theoretical results
indicate that processing time can be reduced by 35% with air injection, although
no commercial application of the technique has yet been undertaken. Another
development aimed at producing a high grade/low volume pregnant solution is
staged heap leaching. The technique involves the leaching of several heaps counter-
currently, with fresh leach solutions being added intermittently to the most depleted
heap. After leaching of a heap is completed, a thorough washing cycle is conducted
to recover additional values. The wash water is replenished with fresh cyanide and
is used to agglomerate a new charge of ore being prepared for heap leaching. The
stage heap leaching has resulted in a pregnant solution containing 4.4 ppm gold
which is significantly higher than that obtained from single stage heap leaching.
Because of the simplicity of compact operation, multiple lifts are becoming more
common. It has been successfully used at Candelaria, Nevada, for several years".
124 A. R. UDUPA. S. K. KAWATRA AND M. S. PRASAD

RECOVERY OF GOLD FROM LEACH SOLUTIONS

Gold from pregnant solutions is recovered either by conventional precipitation with


zinc dust (Merrill-Crewe system) or by recently developed carbon adsorption sys-
tems. Ion-exchange and solvent extraction techniques have also been investigated.
in recent years. Gold from the loaded carbon or resin is generally eluted using hot
caustic solution. From the resulting concentrated solution, gold may be recovered
either by zinc dust cementation or electrowinning methods. The product is then
acid leached and smelted to get doe bullion.
Several modifications of the carbon adsorption system such as carbon-in-leach
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(CIL), carbon in pulp (ClP), and carbon-in-column (ClC) have found wide ac-
ceptance in the last decade. Some developments in carbon-in-pulp (CIP), ion-
exchange and elution techniques are given below.

Carbon-in-pulp Process
Although the use of activated carbon for the recovery of gold from cyanide solution
has been known since 1894, a detailed flow sheet for carbon-in-pulp (CIP) was not
developed until 1961 60• In a typical CIP gold recovery process, granular carbon
(usually between 6 and 16 mesh) is moved counter current to the cyanided pulp
in the adsorption contactors. The loaded carbon is then eluted and the gold and
silver values in the eluate are recovered by electro-winning.
Homestake Mine in South Dakota, the first to adopt this new technology in
1973, treats about 5000 tons of ore per day. The adsorbed gold and silver values
. are recovered by modified Zadra process". An innovation in this process flowsheet
is the use of thermal reactivation of the eluted carbon by heating at 600-650'C in
the absence of air in a rotary kiln before it is recycled.
Sorensen'! suggested the treatment of CIP eluates contaminated with base metals
and in particular copper with sulfuric acid to produce a precipitate containing
virtually all gold, which is then calcined at about 180'C in air before being smelted
with borax at 1I00·C to produce bullion containing 94% gold. The process is
claimed to be less time consuming and simpler to operate compared to electro-
winning. An improvement in the technology for recovery of gold by the CIP process,
which enables the use of high carbon concentrates resulting in a reduced contactor
size, has been developed by Davy McKee63 • This has simplified the operation and
reduced the operating cost significantly. Two such contactors of 3000 tpd capacities
are installed at the Ashanti gold plant in Ghana and a second plant in Brazil".
Another important development in the CIP process is the development of Delko
linear screens by South African plants" to remove unwanted wood fiber from the
circuit: The use of linear screens has removed in excess of 90% of wood fibers,
compared to 50-60% obtained from conventional screening techniques.
Equalized-pressure air-cleaned (EPAC) screens were developed in South Africa
by Mintek 6O ·64 to provide less attrition of carbon and less screen wear. The devel-
opment of draught-tube circulation for stirring the CIP tanks is claimed to ensure
good mixing and suspension of carbon in the pulp minimizing the attrition loss of
carbon'". Models for optimizing .the carbon-in-pulp process to minimize the cost
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 125

have been developed by Menne of Bateman6,.68 and Fleming of Mintek 65.69, both
in South Africa.

lon-exchange
The ion exchange technology for the recovery of gold is relatively new and applied
commercially on a very limited scale. The pioneering work for possible use of ion-
exchange resin for the recovery of gold from cyanide solution was originally initiated
by the U.S. Bureau of Mines, Salt Lake City". Development work on pilot plant
equipment for resin-in-pulp (RIP) process was carried out by Connit Ltd. of South
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Africa". Ivanovskii et al. 72 have reported the use of liquid ion-exchange (solvent)
contained in a porous plastic slab to extract gold cyanide pulps while leaching is
in progress.
The major disadvantages in using resin to recover gold from cyanide solution
are slow loading of gold and the need for a complex elution method. The use of
resin fibers, developed from a polyacrylonite (PAN) derivative (PAN-imidazoline)
and a polybenzimiadazole (PHI) derivative (PHI-alkylamine), in place of resin
beads in ion-exchange columns is claimed to have solved the problem of slow
loading rates". Another development in the recovery of gold from cyanide solution
is the application of neutral polymeric adsorbent such as polyacrylate XAD7 and
XAD8'·. The advantages of these adsorbents are weaker adsorption forces of gold
which result in a simpler elution method, high selectivity for Au(CN)l- complex.
However, these have a much lower gold loading capacity than typical ion-exchange
resins. Hodgkin and EibF5 synthesized and tested gold adsorption properties of
cycloaliphatic, a weak-base resin made from polydiallylamine, and found that it
had a high gold capacity, up to 5 mmollg dry resin, and gold selective properties.

Elution
The original Zadra elution process" for the recovery of gold from loaded carbon
has seen significant improvements over the years. Davidson and Duncanson" in-
troduced a hydrochloric acid pretreatment step to remove CaCO l and nickel cy-
anide from loaded carbon. Ross and co-workers" developed a pressure method
(600 Kpa at 140·C) for stripping gold from activated carbon which considerably
decreased the elution time. Nizamutdinova and Chuvasheva" reported excellent
elution of gold from carbon with anhydrous ammonia under a pressure of about
600 to 1000 Kpa. Heinen and co-workers" eluted 99% of the precious metal values
in 6 hours at a temperature of 80·C as compared to a norm of 50 hours by the
addition of 20% by volume of water soluble alcohol (ethanol or methanol) to the
alkaline cyanide eluent containing 1% NaOH and 0.1% NaCN.
Stone'? discussed a continuous elution process to recover gold from loaded carbon
which operates at elevated temperature and pressure. It is claimed that the process
is simpler to operate than batch processes and offers significant savings in stripping
costs.
The Anglo elution procedure developed and adopted in South Africa'-" elutes
gold in 8-12 hours using deionized water at 100-120°C. In this process, carbon is
126 A. R. UDUPA, S. K. KAWATRA AND M. S. PRASAD

presoaked with 5% w/v NaCN and 1% w/v NaOH solution before using water.
Anglo American Laboratories" found that organic solvents enhanced the rate of
gold stripping. A similar observation was made by the Duval Corporation", which
found that the adddition of 10-20% v/v ethanol or ethylene glycol to the Zadra
system reduced the elution time to around 8-10 hours. Anglo American Labora-
tories eluted 95% of gold with only 30 bed volume at 50·C by presoaking the carbon
with pure isotropic acetone. Muir et alY reported that acetonitrile and aqueous
acetone strip gold in less than 8 hours using 2-3 bed volume at temperatures
between 25-70°C.
A new approach to the elution of gold from a strong-base resin has been de-
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veloped using highly polarized thiocyanate anion". The method is based on the
strong affinity of the resin for the thiocyanate anion which preferentially replaces
the gold cyanide complex. The resin is stripped by converting the thiocyanate anion
into a series of non-electrostatically bound cationic complexes. The complex strip-
ping solution produced is then treated with an alkali or base solution to recover
the thiocyanate, which is reused in the next elution cycle. A full-scale 'plant is
planned in South Africa treating gold slimes-dam-run-off water",

UNCONVENTIONAL L1XIVIANTS

Although cyanide leaching remains the overwhelming option for treating gold ore
because of its economy and process simplicity, cyanide solutions are toxic and their
use poses long term environmental and disposal problems. In addition, cyanide
solution is not efficient in leaching certain classes of gold ores which are considered
refractory to the cyanidation process. Because of this limitation and increasingly
stringent pollution control regulations, use of lixiviants other than cyanide for the
recovery of gold has received considerable attention during the past few years.
Among them, use of thiourea, bromine, thiosulfate, chlorine and iodine are being
seriously investigated. Developments in the use of these lixiviants are described
below.

Thiourea
Gold dissolves in acidic thiourea solution forming a cationic complex. Kazakov et
al. 85 described the gold dissolution reaction as follows:
Au + 2CS(NH,), ----. Au[CS(NH,h)i' + e
Thiourea leaching has been done in hydrochloric, sulfuric or nitric acid 'media
with the addition of oxidants such as formamidine disulfide 86-k8 , hydrogen
peroxide 87•89- 91, sodium peroxide", dissolved oxygen", iron(IIl)86.88-90, ozone 92•93 ,
and manganese dioxide". Lodeischikov et al. 95 reported that the rate of dissolution
of gold is similar in hydrochloric and sulfuric acid media, whereas nitric acid re-
tarded the process. Groenewald" evaluated the thiourea dissolution of gold in
sulfuric acid media containing various oxidants and observed that the addition of
formamidine disulfide, hydrogen peroxide and dissolved oxygen produced identical
DEVELOPMENTS [N GOLD LEACHING: A LITERATURE SURVEY [27

results. The rate of dissolution of gold in a solution containing 0.1 M sulfuric acid,
0.1 M thiourea and 0.01 M formamidine disulfide is as much as 1.1 x 10- 8 cm's ",
which is at least five times faster than is possible with conventional cyanide solutions.
High gold dissolutions were also reported by' Hiskey?" and Filmer et al. 97 from
acidified thiourea leaching using Fe(III) as oxidant (Table III). The initial rate of
dissolution of gold in a freshly prepared acidic thiourea solution containing iron
(III) as oxidant is rapid and is controlled by the rate of diffusion of the oxidant to
the surface of gold. Chen et al. 98 made similar observations and reported that the
rate of dissolution of gold and silver in a leaching solution containing 1.0% thiourea,
0.5% sulfuric acid and 0.1 % ferric ion is over 10 times faster than in a solution
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containing 0.5% sodium cyanide and 0.05% calcium oxide. The use of ozone as
an oxidant has been investigated by Gabra'" and Chtyan", who concluded that
thiourea consumption to dissolve gold was very high. The rate of dissolution of
gold in thiourea solution decreases with time. The high thiourea consumption and
the low rate of dissolution are attributed to an inhibiting coating of sulfur on the
surface of gold particles formed due to the degradation of thiourea". Schulze tOO
described a procedure that effectively reduces the decomposition of thiourea and
avoids the passivation of the feed material. The procedure involves adding S02 to
the leaching solution, thereby controlling the redox couple between thiourea and
its first decomposition product. The role of SO, in controlling the thiourea con-
sumption has also been reported by other investigators'P'<'".
Groenewald'" attributed the fast initial rate of dissolution to the ability of Fe(III)
to retard the dissociation of thiourea and concluded that Fe(III) in sulfate form is

TABLE III
Comparison of gold dissolution in thiourea and cyanide solutions

Initial Reagent Gold


Gold Time Consumption Extraction
Material System (g/t) (hrs) (kg/t of ore) (%) Ref.'

Oxidized CN 1.3 24 2.8 90.0


tailing from TU 1.3 4 5.2 90.0 97
cyanidation
Vnoxidized CN J.2 24 3.0 95.0
tailing from TV J.2 4 90.0
cyanidation
Pyrite CN 3.6 24 3.3 37.0
concentrate TU 3.6 4 10.7 41.0
Run of mine CN 6.9 24 0.7 89.0
ore TV 6.9 4 11.6 87.0
Copper smelter CN 5.83 24 40.0
96
flue dust TV 5.83 4 82.2
autoclave
leach residue

, System used by Filmer et al.":


CN: I gil NaCN. pH 11
TV: 2 gil Thiourea. 1 gil Fe". pH 1.5
System used by Hiskey":
CN: 0.5M CN. pH 9.5
TU: 0.13M Thiourea. 0.U5M Fe"
128 A. R. UDUPA, S. K. KAWATRA AND M. S. PRASAD

much more effective than in a chloride medium, which agrees with the observations
made by Lodeishchikov et a1. 9S
Bliston and co-workers'P studied the leaching of an oxidized gold ore containing
6.1 glt gold and 5.2 glt silver by controlling pH, redox potential and thiourea
concentration. They found that raising either the thiourea concentration or redox
potential increased the rate of gold and silver extraction but also increased the
thiourea consumption. Pyper and Hendrix'?' reported on the leaching of a finely
disseminated gold ore using thiourea solution. Charley'" proposed a three stage
agitated thiourea leach process for treating concentrates and high grade ores.
Bodson'P described a two-step process for treating pyritic material containing
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25 gAult, first at 700·C for 2 hours and then at 400·C for 4 hours before leaching
with acidified thiourea solution (pH = 0.8) containing 20 gil sulfuric acid at 60°C
to extract 99% of gold in 4 hours. The kinetics of gold leaching from pyrite con-
centrates from the Val D'or area in Quebec, Canada, using acidified thiourea were
investigated by Gabra", who found that the gold extraction was of zero order with
respect to Fe (III) and sulfuric acid concentration. The rate of gold dissolution was
first order with respect to thiourea concentration in the range of 1-15 gil and was
independent of thiourea concentration above 15 gil. Hiskey" studied the leaching
characteristics of bulk sulfide concentrates and residues from the autoclave leaching
of smelter flue dust in acidified thiourea solution and reported an extraction of
83% gold and 75% silver in 4 hours from sulfide concentrate by leaching with 1
M CS(NH 2h, 0.5 M H 2S0 4 and 0.5 M Fe(III).
Yen and Wyslouzil'" investigated the dissolution of gold contained in leach
residues produced by pressure oxidation of sulfidic flotation concentrates. Thiourea
leaching of these residues yielded gold extractions equivalent to cyanidation in
much less time and without an intermediate neutralization step.
Deschenes and Ghali 102 studied in detail the thiourea leaching characteristics of
a gold-containing chalcopyrite concentrate. They obtained a maximum gold and
silver extraction of 95.5% and 85.4%, respectively, using hydrogen peroxide as an
oxidant. Maximum recoveries were obtained at a temperature below 40·C and a
pH below 2.0. Wen107 discussed a process for leaching roasted (680·Q flotation
concentrate from carbonaceous clayey gold ores with thiourea at pH 1.5 to 2.0 to
obtain 95% gold extraction. Zegarra et al. 108 investigated the extraction of gold
and silver using thiourea from Mn-Ag ores which are not amenable to direct
cyanidation, and recovered 90% gold and 50% silver. Sandberg and Huiatt'" de-
veloped a process to recover gold and silver from a complex lead-zinc sulfide ore.
The process involves leaching of lead chloride residue with thiourea.
Several investigators advocated pre-leaching of refractory gold ores prior to
thiourea extraction of precious metalsI02.110.111. Moussoulos et al. 111 leached roasted
arsenopyrite ore with sulfuric acid to remove arsenic before treating with thiourea
solution to extract gold and silver. They reported an extraction of more than 95%
gold and over 94% silver by leaching with acidified thiourea solution at ambient
temperature in 90 minutes using air as an oxidant. Deschenes and Ghali l O2 obtained
better extraction of silver by pre-leaching chalcopyrite with sulfuric acid. However,
the additional step increased gold loss and acid consumption. Lodeischikov" ob-
tained a maximum gold recovery of 92-98% after 8 hour leaching in a solution
containing 4 gil thiourea, 5 gil sulfuric acid and 3 gil ferric sulfate.
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 129

Most of the process development work involving thiourea has been aimed at the
leaching step, with limited work focused on the recovery of gold and silver from
thiourea solution. Although processes like cementation'w'P, activated
carbon92.9S,lOO.101.IOS,ll l . lll , ion-exchange resins 92,lOI .lll ,lll- 1l8, and electrowinning'Pr!"
have been tried, additional work is needed to establish a method that offers the
best possibility of recovering precious metal values.

Iodine
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The potential application of iodine solution for the extraction of gold has been
known for many years; however, information on detailed studies is limited in the
literature. Iodine is non-toxic and its halides form the most stable gold complexes
among all the halides of other halogens. It leaches out gold from its ore at low
concentrations and can penetrate rocks particularly well. According to Jacobson
and Murphy'", it does not adsorb on gangue particles to any great extent, allowing
excellent recovery of the reagent, which helps reduce the cost of the process.
The chemistry of gold dissolution in iodine solution is outlined by Hiskey and
Atluri", The main reactions involved are:
I."" + 1- = Ii
The Ij" ion is present when solutions contain more than 1.0 x lO-lM dissolved
iodine. The triiodide serves as an oxidant for gold and dissolution takes place
according to the following electrochemical reactions:
Au + 21- ----+ AuI, + e anodic
1,- + 2e- = 31- cathodic
2Au + 1- + Ii ----+ 2AuI,- overall
The application of iodine for leaching gold is described in a patent by McGrew
and Murphy'", They used a triodide complex obtained by reacting iodine with
iodide to oxidize gold in the ore. The iodide is obtained by reacting saturated
solution of iodine containing natural salt with base metal sulfide in the ore. The
gold is subsequently recovered using activated.carbon. They also demonstrated
that the iodine can readily be regenerated electrolytically in a diaphragm cell.
However, more research and development work is needed to explore the utility
and economics of this reagent.

Bromine
Although bromine has been recognized for many years as a powerful gold extrac-
tant, it is only recently that its application to gold has been seriously examined.
Sergent et al. 124 have proposed the dissolution of gold in bromine as follows:
Br,(DMH) + 2H,O = 2HOBr + H,(DMH)
o
2Au + 3HOBr + 3NaBr = 2AuBr, + 3NaOH
AuBr, + NaBr = Na-(AuBr.)-
130 A. R. UDUPA. S. K. KAWATRA AND M..S. PRASAD

where DMH stands for debromodimethyl hydention. The overall reaction can thus
be represented as,
4Au O + 3Br,(DMH) + lONaBr + 6H,O = 4Na(AuBr,) + 6NaOH + 3H,(DMH)
The natural advantages claimed for bromine are rapid extraction, non-toxicity,
and adaptability to a wide range of pH values. This has been observed by Dadgar
er a1. 125 while comparing bromine leaching of calcined refractory gold ore with the
results from cyanide leaching. The high dissolution rate and low recovery costs of
the bromine process are expected to give a definite economic advantage over
cyanidation even though preliminary laboratory data indicated that the cost of
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reagents for both the processes is about the same 126. Disadvantages are likely to
be high reagent consumption and interference in AA and ICP assay techniques,
although these can be overcome. Active research is being carried out in several
laboratories to study various aspects of bromine leaching; however, full scale com-
mercial exploration is still being awaited.

Other Lixiviants
Application of thiosulfate for the extraction of precious metal has been known for
some time now. Early use of thiosulfate to extract silver was made in the Patera
Process!", In this process, the product from a chloridizing roast is leached with
sodium sulfate-copper sulfate solution. Berezowsky and Sefton!" reported the use
of ammonium thiosulfate to extract gold and silver from sulfide concentrates and
various pressure oxidation leach residues. They concluded that a mild oxidation is
preferable to achieve high extraction rather than a freely oxidative condition in
order to prevent degradation of thiosulfate, hence reducing leaching efficiency.
Similar observations were made by Tozawa and co-workers'" while leaching native
gold from complex sulfide ore using ammoniacal thiosulfate. Kerly'" described an
ammoniacal thiosulfate process to recover gold and silver from ores that are difficult
to treat by cyanidation by maintaining a pH value greater than 7 and sulfite ion'
concentration of at least 0.05%. Flett et a1. 131 reported the chemistry of leaching
of silver sulfide with ammonium thiosulfate-cuprous thiosulfate solutions. They
also observed that the amount of silver that is leached increases with both the
thiosulfate and cuprous sulfate concentrations.
USBM has reported that malononitrile (CN---eH~CN) can leach gold more
effectively than cyanide!", However, its toxicity and strong chelating power dis-
couraged further investigation.

CONCLUSIONS

Because of economics and process simplicity, cyanidation remains the overwhelm-


ing process route for the extraction of gold even today and, looking at the present
trend, this proven lixiviant is going to dominate the gold industry for some time
to come. Between the carbon adsorption and the Merrill-Crowe procedures for
the recovery of gold from pregnant solution, carbon adsorption offers some savings
DEVELOPMENTS IN GOLD LEACHING: A LITERATURE SURVEY 131

in both capital and operating costs and may be applicable to lower grade ores at
lower gold prices. However, the Merrill-Crewe process is currently being used at
many large gold mines around the world and will continue to be in use at these
plants with possible improvements in process control. The activated carbon ad-
sorption process which has been adopted in the last 10 to 15 years will find wider
use in the future. The ClP and ClL processes will continue to find applications in
recovering gold from carbonaceous type refractory ores.
When clay, flotation reagents or hematite fines are present in the ore. ion-
exchange resins may result in better performance than carbon. Resins may also
become attractive for feeds containing significant amounts of silver and other ex-
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pensive base metals such as cobalt. However, the problem of requiring either
solution pH adjustment to an undesirably low level to obtain gold adsorption on
weak base resins, or the difficult stripping of gold loaded on strong base resins.
has to be solved before ion-exchange resins can gain widespread acceptance by the
gold industries.
There have been a number of developments in the area of pre-treatment of
refractory gold ores. Among them, pressure oxidation has attained full commercial
status with some plants already in operation and many more under construction.
Other processes such as flash chlorination. NITROX and ARSENa processes may
find better acceptance. .
Although bio-leaching offers considerable savings in capital cost. there seems to
be no particular savings in operating cost compared to other preoxidation processes
except conventional roasting. However. considerable progress made in solving some
of the technical problems associated with bioleaching of gold ores is expected to
encourage further development and proliferation of the process in the future.
For high clay-bearing ores. which would present problems during percolation in
heap leaching, the agglomeration pretreatment of the crushed ore has been found
to be very helpful. Addition of oxygen improves gold recovery. The subjects of
solution management. control of dissolution, and selective recovery of desirable
metals. and heap construction could be potential research areas with respect to
heap leaching practice.
The use of leachants other than cyanide for the recovery of gold has attracted
many investigators mainly due to the potential environmental restraints on the use
of cyanide and also the refractoriness of certain ores to conventional cyanidation.
Many reagents that form stable complexes with gold, e.g .. thiourea. thiosulfate,
halides, malononitrile, acetonitrile and polysulfides, have been investigated. De-
spite the number of research papers. operations using alternative leachants are
limited. Additional research has to be carried out on these reagents both in the
area of leaching and in reagent recovery techniques to establish an integrated
alternative method that offers the best possibility of recovering precious metal
values.

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