UNIVERSITY LOGO

FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING.

PROJECT TITLE

Ammonia pre-treatment of copper rich gold ore at Bulawayo Mining Company (How Mine) for
the elimination of copper interferences prior to cyanidation

RESEARCHER

TARIRO TECLA MOTO

SUPERVISOR(S)
1.0 Background.

How mine is a gold mine owned by Metallon Gold Zimbabwe (Pvt) Ltd, a subsidiary of
Metallon Corporation of South Africa. The mine is located in the Bulawayo Greenstone Belt in
Matabeleland South Province. Metallon Gold Zimbabwe holds a Mining Lease that covers the
area formerly occupied by claims that formed the How Mine property. The area covered by the
lease was surveyed and declared to be 2,587 hectares.

How mine is located 32 km southeast of the city of Bulawayo in Matabeleland South Province,
in the Bulawayo Mining District of Zimbabwe. How mine is linked with the city of Bulawayo by
a narrow tarred road that branches off from the Old Esigodini Road. Disused gravel roads and
footpaths connect the mine with the local rural communities and commercial farming areas. The
city of Bulawayo is the major commercial Centre in the Matabeleland region and is serviced by
an international airport.

In the leaching tanks a 𝑪𝑵 strength of 0.1% and a 𝒑𝑯 of at least 11 is used. There are a total of
18 tanks which incorporate both the CIP and CIL processes. Tanks 1 to 6 have a volume 140m3
tank 7 to 14 have a volume of 80m3 and tank 14 to 18 have a volume of 180m3. Compressed air
is added in the tanks and the pulp density in leach tank 1 is expected to be between 49-52%
solids. Double impeller agitators are being used for mixing. Anglo American Research
Laboratory elution method is being used in the stripping of gold from loaded carbon. Eluted
carbon is treated through thermal regeneration before being returned to the adsorption circuit.
Adsorption leach residue is delivered to the tailings. After electro-winning, cathode digestion is
being done with (50-60) % strength HNO3 to remove copper and then the smelted bullion is then
sold to Fidelity Printers and Refinery. For the financial year 2022 (April 2021 to date) they are
experiencing an average recovery of 71% against a target of above 78% and a production output
of (70-80) kg of gold per month. The average monthly recovery is actually less that the
yesteryear target of 85% partly due the declining grade. The recoveries are limited due to
detrimental effect of copper which forms highly stable complexes with cyanide, leading to
excessive cyanide consumption and hence poor extractions of gold when sufficient level of
cyanide to counterpart copper impact is not provided (Bas, et al., 2012). The solubility of copper
minerals in 0.1% Sodium Cyanide (𝑵𝒂𝑪𝑵) solution is shown in Table 1. According to (Muir,
2011) he reported that every 1% of reactive copper present in the ore consumes 30kg/t 𝑵𝒂𝑪𝑵,
which adversely affects the process economics.

1.1 Problem statement

How Mine (Bulawayo Mining Company) is failing to meet their 2021-2022 target of
maintaining above 78% gold recovery due to the presence of copper in the ore which has higher
affinity of cyanide than gold. This existence of copper has led to an overall increase in cyanide
consumption of about 22% at US$ 2.96/kg, which translates to a cost of US$ 353,320 per year.
Copper is ultimately reducing gold bullion fineness, resulting in gold fetching lower price on the
market. It is on this basis that this research is imperative in finding ways of mitigating this
problem.

1.2 Justification of study

This study will benefit in the following,

 Reduction of company losses (which is around US$ 353,320 per year) emanating from
high cyanide consumption by copper in ore hence, higher leaching efficiencies and gold
output since more of cyanide will be complexing with gold.
  Downstream processes like activated carbon adsorption and elution will be enhanced by
the elimination considerable amount of copper
 Purity of the gold bullion increases by removal copper which is an impurity, this implies
that the market price of the gold bullion will significantly rise.
 The study will add new knowledge to the academic board of knowledge on how to
process copper-rich gold ores at BMC.

It is therefore necessary to explore a cost-effective way to eliminate copper interferences in the

operation so as to enhance leaching efficiencies and downstream processes as well as gold
bullion fineness which is currently around 82%.

1.3. Aim

 The aim is to mitigate copper interferences on gold extraction from refractory copper-rich
gold ores so as to enhance leaching efficiency and overall plant recovery.

1.4. Objectives

 To determine optimum ammonia (𝑵𝑯𝟑) concentration in the pre-treatment step,

 To determine optimum temperature conditions in the ammonia leach pre-treatment step,
 To determine the effect of cyanide concentration on gold dissolution in the cyanidation
step,
 To determine the effect of ammonia on cyanide consumption and leaching efficiency of
gold into solution.
 Literature review

Cyanide leaching of copper containing gold ores

Due to decreasing resources of amenable cyanide extractable deposits of gold, in 21st

century a massive percentage of gold will be recovered from refractory gold ores, of
which numerous of these complex ores of gold encompasses soluble copper minerals.
Twenty percent of all deposits of gold was projected to have substantial mineralization
of copper, usually accompanied with chalcopyrite, tennantite, tetrahedrite and
chalcocite and bornite in definite ores (Muir, et al., 1989).

When gold ores accompanied with copper minerals are cyanide leached for the
recovery of gold copper is a problem because it selectively dissolute to form stable
copper cyanide complexes. Hence, excessive consumption of cyanide results to poor
extractions of gold when acceptable cyanide level is not available (Bas, et al., 2012).

(Muir, 2011), stated that every one percent reactive copper available in the ore
consumes 30kg/t sodium cyanide, which unfavorably affects the process efficiencies.
Cyanide consumption can be even higher than the above stated values due to the
formation of cyanate and thiocyanate in addition to copper cyanide complexes. (Muir,
et al., 1991) pointed out that 0.5% 𝑪𝒖 as the benchmark for cyanide leaching of copper
containing gold ores.

Processing options of copper-rich gold ores

Significant investigation for processing of copper containing gold ores has been
investigated. Proposed or developed treating options over the years can be classified
into four technologies i.e. copper cyanide, ore selective leaching technologies, copper
cyanide distraction technologies and segregation technologies.

Ore segregation technologies

To isolate high grade bearing ores from low copper containing ores, discriminatory
mining method has been employed. Ores with not as much as 0.5% copper can be
selectively mined and cyanide leached, high grade copper ores being stockpiled for
future treatment. For the production of concentrates of high-grade copper for smelting,
floatation is a widely used technology for processing of primary copper rich gold ores
(Dai, et al., 2011).

Selective leaching technologies

Selective leaching copper before gold cyanidation is the first option using leaching
agents such as dilute acid, Chloride or Ammonia (Muir, et al., 1989). Nevertheless, for
the treatment of low-grade copper ores these developments are often inefficient,
predominantly sulphidic ores due to high consumption of the reagent, issues with the
recovery of leached copper and potential neutralization before cyanidation.

Choosing a reagent which is selective for gold over copper is another option or to
choose mixture of reagent and conditions that promotes insolubility of copper minerals.
For the treatment of copper bearing gold ores, a series of studies have been done on the
implementation of ammonia-cyanide process (Costello, et al., 1992).

When ammonia is added to cyanide solution it reduces cyanide consumption and

increase the gold selectivity over copper in the leaching process. Other selective
approaches include leaching with 𝑩𝒓𝟐 by the K process (Sehic, 1988) and leaching
with thiourea (Chen, et al., 1980), though neither of these processes has been adopted
commercially.

Copper cyanide destruction technologies

The Inco 𝑺𝑶𝟐/air process is the most widely adopted technique for the handling of
cyanidation tails (Robbins, 1996). This process encompasses the use of sulphur dioxide
(𝑺𝑶𝟐) or other source of sulphate, which reacts with copper cyanide and oxygen,
resulting in the formation of cyanite due to the oxidation of cyanide. Copper is
precipitated out as 𝑪(𝑶𝑯)𝟐 at the end of the reaction. Alternative destruction processes
include hydrogen (Degussa process), alkaline chlorination, , Caro’s acid, photolysis,
electrochemical oxidation, ultrasonic and biodegradation. Among these destruction
processes, Caro’s acid, alkaline chlorination, hydrogen peroxide and biodegradation
Among these, alkaline chlorination, hydrogen peroxide, Caro’s acid and biodegradation
are the main processes which have been applied in industry.
Copper cyanide recovery technologies

Researches have been conducted for the investigations on the use of several materials
for the recovery and adsorption copper cyanide. A vital characteristic of these
adsorbents is that due to poor selectivity/adsorption of free cyanide ions, free cyanide
ions are not recovered to any considerable extent. Thus, a lot of the methods combine
the addition or recycle of metal, metal ions or metal salts to form complexes with free
cyanide ions and enable free cyanide recovery.

The recovery of cyanide and copper actually offers both environmental and economic
benefits and therefore, it might be a more attractive option relative to destruction. A
variety of processes have been advanced over the years, for the recovery of copper
and/or cyanide. These comprises of acidification-based techniques like AVR
(acidification, volatilization and re-neutralization) and SART (sulfidisation,
acidification, recycling, and thickening), direct electro-winning, activated carbon, ion
exchange resins, solvent extraction, poly-chelating polymers and membrane
technologies. A typical example of sulfidisation is shown in the following equation,

𝟐𝑪𝒖(𝑪𝑵)𝟐𝟑− + 𝑺𝟐− + 𝟔𝑯+ → 𝑪𝒖𝟐𝑺 + 𝟔𝑯𝑪𝑵

Chemistry of copper in cyanide and Ammonia solutions

Copper cyanide chemistry

Various copper and cyanide species exist for a copper cyanide aqueous system. The
equilibrium of these species can be described by the following reactions (Lu, et al.,
2002):

𝑪𝒖+ + 𝑪𝑵− ⇌ 𝑪𝒖𝑪𝑵(𝑺)

𝑪𝒖𝑪𝑵 + 𝑪𝑵− ⇌ 𝑪𝒖𝑪𝑵−𝟐

𝑪𝒖𝑪𝑵−𝟐 + 𝑪𝑵− ⇌ 𝑪𝒖𝑪𝑵𝟐𝟑−

𝑪𝒖𝑪𝑵𝟐𝟑− + 𝑪𝑵− ⇌ 𝑪𝒖𝑪𝑵𝟑𝟒−

𝑯+ + 𝑪𝑵− ⇌ 𝑯𝑪𝑵(𝒍) ⇌ 𝑯𝑪𝑵(𝒈)

Figure presents the 𝑬𝒉 − 𝒑𝑯 diagram for the copper-cyanide-water system. Under typical gold
cyanidation conditions, it is clearly shown that there is a large area of predominance of 𝒖𝑪𝑵𝟐𝟑−.
However, in the presence of hypersaline waters, it has been shown by (Lukey, et al., 1999) that
the predominant species are 𝑪𝒖𝑪𝑵𝟑𝟒−.

𝑪𝒖 − 𝑪𝑵 − 𝑯𝟐𝑶 system 𝑬𝒉 − 𝒑𝑯 diagram at 25 °C (Osseo-Asare, et al., 1984).

The specification of copper cyanide as a function of pH is shown in Figure 13. The domination
of
𝐶𝑢𝐶𝑁43− at alkaline 𝒑𝑯 is clearly presented and also the formation of 𝐶𝑢𝐶𝑁2− is
favoured at low 𝒑𝑯. At high 𝒑𝑯 𝑪𝒖𝑪𝑵𝟐𝟑− formation is favoured. Thus, depending on
the 𝒑𝑯 any of the three aqueous copper species will be present.

Influence of pH on the distribution of copper-cyanide species (Marsden & House,

2006).

High consumption of cyanide during the copper bearing gold ore cyanidation is because of
one or more of the factors below:

i. Copper forms complexes of high coordination numbers with cyanide (Equation

31-33),
 𝐶𝑢𝐶𝑁32− in particular.

ii. Cyanide is oxidised by oxygen to cyanate by the following reaction which is

catalysed by copper, particularly in the presence of activated carbon.

𝟑𝑪𝑵− + 𝟐𝑶𝟐 + 𝑯𝟐𝑶 ⟶ 𝟑𝑪𝑵𝑶 + 𝟐𝑶𝑯− + 𝒆−

iii. Additional cyanide oxidation to cyanate occurs for the case of copper (II)
containing ores as a result of copper (II) reduction during dissolution.

iv. Copper bearing gold ores are normally related to sulphides, some of which can
readily undergo oxidation and form thiocyanate after a reaction with cyanide via
equation 36:

𝑪𝑵− + 𝑺𝟐− ⟶ 𝑺𝑪𝑵− + 𝟐𝒆−

Chemistry of copper in ammonia solutions

Copper minerals reacts with ammonia as shown in the following equations:

𝟐𝑪𝒖𝟐𝑺 + 𝑶𝟐 + 𝟖𝑵𝑯𝟑 + 𝟐𝑯𝟐𝑶 ⇌ 𝟐𝑪𝒖𝑺 + 𝟐[𝑪𝒖(𝑵𝑯𝟑)𝟒]𝟐+ + 𝟒𝑶𝑯−

𝑪𝒖𝑺 + 𝟐𝑶𝟐 + 𝟒𝑵𝑯𝟑 ⇌ [𝑪𝒖(𝑵𝑯𝟑)𝟒]𝟐+ + 𝑺𝑶𝟒𝟐−
𝟒𝑪𝒖𝑭𝒆𝑺𝟐 + 𝟏𝟕𝑶𝟐 + 𝟐𝟒𝑵𝑯𝟑 + 𝟒𝑯𝟐𝑶 ⇌ 𝟒[𝑪𝒖(𝑵𝑯𝟑)𝟒]𝟐+ + 𝟐𝑭𝒆𝟐𝑶𝟑 + 𝟖𝑺𝑶𝟒𝟐− + 𝟖𝑵𝑯𝟒
 Proposed methodology

3.1. Introduction

This chapter describes the proposed steps which are to be taken to determine the effect of
ammonia pre-treatment on the efficiency leaching of gold into solution by the convectional
cyanidation process.
Proposed Ammonia pre-treatment procedure

Ammonia pre-treatment it is to be done under atmospheric conditions before

convectional cyanidation so as to eliminate more of copper which contend with gold on
cyanide and thus reducing gold leaching efficiency. To attain 50% solids concentration,
a known sample mass (80% passing 75µm) of the ore is to mixed with an equal
volume of the water. Ammonia concentration is to be varied from 0.5 to 2M. Agitation
is to be achieved by using the bottle roll system for 24hrs. Sulphuric acid and lime are
to be used as pH regulators. Samples are to be collected at regular time intervals,
filtered so as to obtain clear solutions and are to be analyzed for gold and copper
concentrations using Atomic adsorption spectrometry (AAS) machine. The residual
solids after 24 hours are to be collected for convectional cynidation process to
determine effect of the pre-treatment procedure.

Proposed Cyanidation of pre-treated residue.

To obtain the optimum cyanide concentration a known mass of pre-treated residue

sample is to be leached using bottle roll system for agitation at atmospheric conditions
whilst varying sodium cyanide concentrations for 24hours. Representative samples are
to be collected at regular time intervals and filtered to get a clear solution for assaying
gold and copper concentrations to obtain the optimum time for extraction. The solids
tails for cynidation process are assayed for the extracted gold and copper.
The diagram below shows a schematic view of the proposed methodology for the
project.
Leaching experiments and variables.

Leaching Experiment Variables

Direct cyanidation Cyanide concentration

Ammonia pre-treatment Ammonia concentration & temperature

Pre-treatment residue leaching Cyanide concentration